r 


REESE  LIBRARY 
UNIVERSITY  OF  CALIFORNIA. 


-  '1  ccessious  No. 


•K S; ":/ 


GAS  AND  FUEL  ANALYSIS 
FOR  ENGINEERS. 


A  COMPEND  FOR  THOSE  INTERESTED  IN  THE 
ECONOMICAL  APPLICATION  OF  FUEL. 


PREPARED  ESPECIALLY  FOR  THE  USE  OF  STUDENTS 

at  the 
MASSACHUSETTS  INSTITUTE  OF  TECHNOLOGY. 


BY 


AUGUSTUS  H.  GILL,  S.B.,  PH.D., 

Assistant  Professor  of  Gas  Analysis  at  the 
Massachusetts  Institute  of  Technology,  Boston,  Mass. 


FIRST    EDITION. 

FIRST    THOUSAND. 


NEW   YORK: 

JOHN     WILEY     &     SONS. 

LONDON:   CHAPMAN   &   HALL.    LIMITED. 

1896. 


<n 


Copyright,  1896, 

BY 

AUGUSTUS  H.  GILL. 


ROBERT   DRUMMOND,   ELECTROTYPER   AND   PRINTER,    NEW  YORK. 


. 


PRE 


THIS  little  book  is  an  attempt  to  present  in  a  con- 
cise yet  clear  form  the  methods  of  gas  and  fuel  analy- 
sis involved  in  testing  the  efficiency  of  a  boiler  plant. 
Its  substance  was  given  originally,  in  the  form  of 
lectures  and  heliotyped  notes,  to  the  students  in  the 
courses  of  Chemical,  Mechanical,  and  Electrical  En- 
gineering, but  in  response  to  requests  it  has  been 
deemed  expedient  to  give  it  a  wider  circulation. 

At  the  time  of  its  conception,  nothing  of  the  kind 
was  known  to  exist  in  the  English  language ;  in 
German  we  now  have  the  excellent  little  book  of  Dr. 
Ferdinand  Fischer,  "  Taschenbuch  fur  Feuerungs- 
Techniker." 

The  present  book  is  the  result  of  six  years'  experi- 
ence in  the  instruction  of  classes  of  about  one  hun- 
dred students.  It  is  in  no  sense  a  copy  of  any  other 
work,  nor  is  it  a  mere  compilation.  The  author  has 
in  every  case  endeavored  to  give  credit  where  any- 
thing has  been  taken  from  outside  sources ;  it  is,  how- 

iii 


IV  PREFA  CE. 

ever,  difficult  to    credit    single  ideas,  and    if   he    has 
been  remiss  in  this  respect  it  has  been  unintentional. 

The  study  of  flue-gas  analysis  enables  the  engineer 
to  investigate  the  various  sources  of  loss ;  and  if  this 
compend  stimulates  and  renders  easy  such  investiga- 
tion, the  writer's  purpose  will  have  been  accomplished. 
The  necessary  apparatus  can  be  obtained  from  the 
leading  dealers  in  New  York  City. 

The  author  wishes  to  acknowledge  his  indebtedness 
to  our  former  Professor  of  Analytical  Chemistry,  Dr. 
Thomas  M.  Drown,  and  to  Mrs.  Ellen  H.  Richards, 
by  whose  efforts  the  department  of  Gas  Analysis  was 
established. 

He  will  also  be  grateful  for  any  suggestions  or  cor- 
rections from  the  profession. 

MASSACHUSETTS  INSTITUTE  OF  TECHNOLOGY, 
BOSTON,  November,  1896. 


UNIVEKSITY 

CONTENTS. 

CHAPTER  I.  PAGE 

INTRODUCTION.  SAMPLING — Sampling-tubes.  SUCTION  APPA- 
RATUS. GAS-HOLDERS  i 

CHAPTER  II. 
APPARATUS  FOR  THE  ANALYSIS  OF  CHIMNEY  GASES.   Apparatus 

of  Orsat,  Bunte,  and  Elliott II 

CHAPTER  III. 
THE  MEASUREMENT   OF  TEMPERATURE.      Thermometers — Le 

Chatelier  Pyrometer — Metals  and  Salts 24 

CHAPTER  IV. 

CALCULATIONS.  "  Pounds  of  Air  per  Pound  of  Coal,"  and 
Percentage  of  Heat  Carried  off  by  the  Flue-gases.  Loss 
due  to  Formation  of  Carbonic  Oxide.  Loss  due  to  Un- 
consumed  Fuel 27 

CHAPTER  V. 

PREPARATION  OF  REAGENTS  AND  ARRANGEMENT  OF  THE  LABO- 
RATORY   34 

CHAPTER  VU 

FUELS,  SOLID,  LIQUID  AND  GASEOUS:  THEIR  DERIVATION  AND 
COMPOSITION 40 

CHAPTER  VII. 

FUELS.  METHODS  OF  ANALYSIS  AND  DETERMINATION  OF  THE 
HEATING  VALUE.  Determination  of  the  Various  Constit- 
uents. The  Mahler  Bomb  and  Junker  Gas-calorimeter  50 

APPENDIX. 
TABLES 79 

v 


LIST  OF  ILLUSTRATIONS. 


FIG.  PAGE 

1.  Gas  Sampling-tube •  3 

2.  Sampling  Apparatus .  4 

3.  Sampling  Apparatus  for  Mine-gases 5 

4.  Gas-tube 5 

5.  Richards's  Jet-pump 8 

6.  Bunsen's  Pump 8 

7.  Steam  Air-pump 9 

8.  Orsat  Gas  Apparatus 12 

9.  Bunte  Gas  Apparatus 17 

10.  Elliott  Gas  Apparatus 21 

11.  Melting-point  Boxes 26 

12.  Muencke's  Aspirator 38 

13.  Combustion-furnace 51 

14.  Mahler  Bomb 58 

15.  Mahler  Bomb  and  Calorimeter 59 

16.  Junker  Gas-calorimeter,  section 70 

17.  Junker  Gas-calorimeter        71 

vii 


GAS  AND  FUEL  ANALYSIS. 


CHAPTER   I. 
INTRODUCTION   AND   METHODS   OF  SAMPLING. 

UNTIL  within  recent  years,  the  mechanical  engineer 
in  testing  a  boiler  plant  has  been  compelled  to  con- 
tent himself  with  the  bare  statement  of  its  efficiency, 
little  or  no  idea  being  obtained  as  to  the  apportion- 
ment of  the  losses.  Knowing  the  composition  and 
temperature  of  the  chimney-gases  and  the  analysis  of 
the  coal  and  ash,  the  loss  due  to  the  formation  of  car- 
bonic oxide,  to  the  imperfect  combustion  of  the  coal, 
to  the  high  temperature  of  the  escaping  gases,  can 
each  be  determined  and  thus  a  basis  for  their  reduc- 
tion to  a  minimum  established. 

By  the  simple  analysis  of  the  chimney-gases  and 
determination  of  their  temperature,  a  very  good  idea 
of  the  efficiency  of  the  plant  can  be  obtained  previous 
to  making  the  engineering  test.  For  example,  in  a 
test  which  the  author  made  in  connection  with  his 
students,  the  efficiency  was  increased  from  58  to  70 
per  cent,  upon  the  results  of  the  gas  analysis  alone. 


GAS  AND   FUEL   ANAL  YSIS. 

To  this  end  a  representative  sample  must  be  collected 
according  to  the  method  about  to  be  described. 

SAMPLING. 

Before  proceeding  to  take  a  sample  of  the  gas,  the 
plant — for  example,  a  boiler  setting — from  which  the 
gas  is  to  be  taken  should  be  thoroughly  inspected, 
and  all  apertures  by  which  the  air  can  enter,  carefully 
stopped  up.  A  suitable  tube  is  then  inserted  air-tight 
in  the  gas-duct,  connected  with  the  sampling  or  gas 
apparatus,  and  suction  applied,  thus  drawing  the  gas 
out.  Cork,  putty,  plaster  of  Paris,  wet  cotton-waste, 
or  asbestos  may  be  used  to  render  the  joint  gas-tight. 
The  place  of  insertion  should  be  chosen  where  the  gas 
will  be  most  completely  mixed  and  least  contaminated 
with  air.  The  oil-bath  containing  the  thermometer  is 
similarly  inserted  near  the  gas-tube,  and  the  tempera- 
ture read  from  time  to  time. 

I.  Tubes. — The  tubes  usually  employed  are  Bohe- 
mian-glass combustion  tubing  or  water-cooled  metal 
tubes;  those  of  porcelain  or  platinum  are  also  some- 
times used.  Glass  and  porcelain  tubes  when  subjected 
to  high  temperatures  must  be  previously  warmed  or 
gradually  inserted:  the  former  may  be  used  up  to 
temperatures  of  600°  C.  (1200°  F.).  Uncooled  metal 
tubes,  other  than  those  of  platinum,  should  under  no 
circumstances  be  used.* 

*  Fischer,  "Technologic  der  Brennstoffe,"  1880,  p.  221,  states 
that  the  composition  of  a  gaseous  mixture  was  changed  from  1.5 
to  26.0  per  cent  carbon  dioxide,  by  the  passage  through  an  iron 
tube  heated  to  a  dull  red  heat,  the  carbonic  oxide  originally 
present  reducing  the  iron  oxide  with  the  formation  of  carbon 
dioxide. 


IN TR OD  UCTION  A  ND  ME  THOD  S  OF  SA  MPLING.      3 

The  metal  tube  with  the  water  cooling  is  made  as 
shown  in  Fig.  I,  c  being  a  piece  of  brass  pipe  3 
feet  long,  \\  inches  outside  diameter,  b  the  same 
length,  \  inch  in  diameter,  and  a  \  inch  in  diameter. 
The  water  enters  at  d  and  leaves  at  e.  The  walls  of 


FIG.  i.— GAS-SAMPLING  TUBE. 

the  tubes  are  TV  inch  thick.  The  joint  at  A  should 
be  brazed;  the  others  may  be  soldered. 

Platinum  tubes  from  their  high  cost  and  small  bore 
are  seldom  used ;  they  are  attacked  by  carbon,  cyan- 
ogen, arsenic,  and  metallic  vapors. 

2.  Apparatus  for  the  Collection  of  Samples. — 
A  convenient  sampling  apparatus  is  shown  in  Fig.  2. 
It  may  be  made  from  a  liter  separatory  funnel — in- 
stead of  the  bulb  there  shown — fitted  with  a  rubber 
stopper  carrying  a  tube  passing  to  the  bottom  and  a 
T  tube;  both  of  these,  except  where  sulphur-con- 
taining gases  are  present,  can  advantageously  be 
made  of  y^-inch  lead  pipe.  The  stopper  should  not 
be  fastened  down  with  wire  between  the  tubes  after 
the  manner  of  wiring  effervescent  drinks,  as  this 
draws  the  rubber  away  from  the  tubes  and  occasions 
a  leak.  The  fastening  shown  consists  of  a  brass  plate 
fitting  upon  the  top  of  the  stopper,  provided  with 
screws  and  nuts  which  pass  through  a  wire  around 


4  GAS  AND    FUEL   ANALYSIS. 

the  neck  of  the  separatory.      A  chain  fastened  to  the 
plate  serves  as  a  convenient  method  of  handling  it. 

In  using  the  apparatus,  the  bulb  is  filled  with  water 
by  connecting  the  stem  with  the  water-supply  and 
opening  one  of  the  pinchcocks  upon  the  T  tube;  the 


FIG.  2. — SAMPLING  APPARATUS. 

water  thus  entering  from  the  bottom  forces  the  air 
out  before  it.  One  branch  of  the  T  is  connected  with 
the  sampling-tube  and  the  other  with  the  suction- 
pump,  the  stopcocks  being  open,  and  a  current  of  gas 
drawn  down  into  the  pump;  upon  opening  the  cock 
upon  the  stem,  the  water  runs  out,  drawing  a  small 
portion  of  the  gas-current  passing  through  the  T  after 
it  into  the  bulb.  It  is  then  taken  to  a  convenient 


INTRODUCTION  AND  METHODS  OF  SAMPLING.      $ 

place  for  analysis,  the  tube  h  connected  with  a  head  of 
water,  a  branch  of  the  T  i,  with  the  gas  apparatus,  and 
a  sample  of  gas  forced  over  into  the  letter  for  analysis. 


FIG.  4. — GAS-TUBE.      FIG.  3. — SAMPLING  APPARATUS  FOR 

MINE-GASES. 

Enough  water  should  be  left  in  the  bulb  to  seal  the 
stopcock  on  the  bottom  and  prevent  leakage.  This 
apparatus  is  better  adapted  for  the  needs  of  the  class- 


O  GAS  AND   FU-EL   ANALYSIS. 

room  than  for  actual  practice,  as  it  enables  the  same 
sample  to  be  given  to  eight  or  ten  students.  As  has 
been  shown  by  several  years'  experience,  the  water 
exercises  no  appreciable  solvent  action  upon  the 
gaseous  mixture  in  the  time — about  half  an  hour — 
necessary  to  collect  and  distribute  the  samples.  It  is 
often  necessary  to  attach  about  a  yard  of  J-inch 
rubber  tubing  to  the  stem  of  the  bulb  to  prevent  air 
being  sucked  up  through  it  when  taking  a  sample. 

In  the  actual  boiler-test  it  is  preferable  to  insert  a 
T  instead  of  this  apparatus  in  the  gas-stream,  connect 
the  gas  apparatus  to  the  free  branch  of  this  T,  and 
draw  the  sample.  In  making  connections  with  gas 
apparatus  the  air  in  the  rubber  connectors  should  be 
displaced  with  water  by  means  of  a  medicine- 
dropper. 

In  the  Saxon  coal-mines,  zinc  cans  of  ten  liters 
capacity,  of  the  form  shown  in  Fig.  3,  are  used  by 
Winkler  for  sampling  the  mine-gases;  they  are  carried 
down  filled  with  water  and  this  allowed  to  run  out, 
and  the  gas  thus  obtained  brought  into  the  laboratory 
and  analyzed.  Small  samples  of  gas  may  very  well  be 
taken  in  tubes  of  100  cc.  capacity  like  Fig.  4,  the 
ends  of  which  are  closed  with  rubber  connectors  and 
glass  plugs.  Rubber  bags  are  not  to  be  recommended 
for  the  collection  and  storage  of  gas  for  analysis,  as 
they  permit  of  the  diffusion  of  gases,  notably  hydro- 
gen. 

3.  Apparatus  for  Producing  Suction. — I.  WATER- 
PUMPS — (a)  Jet-pumps,  depending  for  their  action 
upon  a  considerable  head  of  water,  and  (b)  those 
depending  rather  upon  a  sufficient  fall  of  water. 


IN  TROD  UCTION  AND 

(a)  Jet -pumps. — The  Richards'^jet  pUfflfT*  is  shown 
in    section    in    Fig.    5    and   much    resembles   a   boiler 
injector;  it  consists  of  a  water-jet  w,  a  constriction  or 
waist  a,  a  waste-tube  0,  and  a  tube  for  the  inspiration 
of  air.     The  jet  of  water  forms  successive    pistons 
across  a,  drawing  the  air  in  with  it  and  is  broken  up 
into  foam  by  the  zigzag  tube  o. 

This  pump  is  known  in  Germany  as  Muencke's,  and 
in  England  as  Wing's;  Chapman's  pump  is  also  a 
modified  form. 

It  may  be  easily  constructed  in  glass,  the  jets  pass- 
ing through  rubber  stoppers  which  are  wired  down, 
thus  admitting  of  adjustment  to  the  conditions  under 
which  it  has  to  work. 

(b)  Fall-pumps. — Bunsen's  pump,   Fig.  6,   consists 
of  a  wide  glass  tube  A,  drawn  out  at  the  bottom  for 
connection  with  a  £-inch  lead  pipe  £,  and  at  the  top 
for  connection  with  cy  the  tube  through  which  the  air 
is  drawn;  this  tube  is  usually  fused  in,   although   it 
may  be  connected   with  rubber;  a  is  a  rubber  tube 
provided  with  screw  cocks  connected  with  the  water- 
supply;  d  is  connected  with  a  mercury  column,  and 
the  vessel  B  serves   for   the  retention   of  any  water 
which  might  be  drawn  back  into  the  apparatus  evac- 
uated. 

The  tube  b  for  the  best  results  should  be  32  feet  in 
length,  equal  to  the  height  of  a  column  of  water  sup- 
ported by  the  atmosphere,  although  for  the  ordinary 
purposes  of  gas-sampling  it  may  be  shorter. 

When  water  is  admitted  through  a  it  fills  b,  acting 

*  Richards,  Am.  Jour,  of  Science  (3),  8,  412;  Trans,  Am.  Inst, 
Min.  Engrs.,  6,  492. 


8 


GAS  AND   FUEL   ANALYSIS. 


as  a  continually  falling  piston  drawing  the  current  of 
air  through  e  and  its  connections.  These  various 
forms  of  water-pumps  should  give  a  vacuum  repre- 


V^ATER 


FIG.  5. — RICHARDS'  JET-PUMP.       FIG.  6. — BUNSEN'S  PUMP. 

sented  by  the  height  of  the  barometer  less  the  tension 
of  aqueous  vapor  at  the  temperature  at  which  they 
are  used,  or  about  29  inches  of  mercury. 


INTRODUCTION  AND  METHODS  OF  SAMPLING.      9 

II.  STEAM-PUMPS. — Kochinke  describes  the  appa- 
ratus in  use  in  the  Muldner  Hutten  in  Freiberg, 
shown  at  one-fifth  size  in  Fig.  7.  It  consists  of  a 
glass  tube  drawn  down  to  an  opening  6  mm.  in  diam- 


FIG.  7. — STEAM  AIR-PUMP. 

eter;  concentric  with  this,  and  held  in  place  by  the 
washer  a,  is  the  steam-jet  2  mm.  in  diameter,  passing 
through  the  cork  b,  the  cement  c,  and  covering  d.  It 
is  connected  with  the  steam-pipe  at  g  by  webbed 
rubber  tubing/;  the  air  enters  at  e.  This  is  said  to 
give  very  good  results  and  be  economical  in  use  of 
steam. 

In  case  neither  water  nor  steam  be  available, 
recourse  must  be  had  to  the  ordinary  rubber  syringe- 
bulbs,  provided  with  suitable  valves,  obtainable  at  any 
rubber  store,  or  to  a  bottle  aspirator.  This  consists  of 
two  one-gallon  bottles,  provided  with  doubly  perfor- 
ated rubber  stoppers,  carrying  tubes  of  glass  or  lead 
bent  at  right  angles.  In  each  bottle  one  of  these  tubes 
passes  nearly  to  the  bottom,  and  these  are  connected 
together  by  a  piece  of  rubber  tubing  a  yard  long, 
carrying  a  screw  pinchcock.  The  other  tube  in  each 
case  stops  immediately  under  the  stopper.  Upon 
filling  one  of  the  bottles  with  water,  inserting  the 
stopper  and  blowing  strongly  through  the  short  tube, 
water  will  fill  the  long  tubes  thus  forming  a  siphon, 


10  GAS  AND   FUEL   ANALYSIS. 

and  upon  lowering  the  empty  bottle,  a  current  of  air 
will  be  sucked  in  through  the  short  tube  originally 
blown  into ;  this  may  be  regulated  by  the  screw 
pinchcock. 


CHAPTER   II. 

APPARATUS    FOR    THE    ANALYSIS   OF    CHIMNEY- 
GASES. 

IN  the  writer's  opinion  the  apparatus  which  is  best 
adapted  for  this  purpose  is  that  of  Orsat;  it  is  readily 
portable,  not  liable  to  be  broken,  easy  to  manipulate, 
sufficiently  accurate,  and — in  the  modification  about  to 
be  described — always  ready  for  use,  there  being  no 
stopcocks  to  stick  fast. 

As  the  Bunte  and  Elliott  apparatus  are  also  used 
for  this  purpose,  they  too  will  be  described. 

Fischer's  apparatus,  using  mercury,  is  rather  too 
difficult  for  the  average  engineer ;  Hempel's  apparatus 
for  the  analysis  of  illuminating-gas  might  also  be  used ; 
it  is,  however,  not  customary. 

ORSAT   APPARATUS. 

Description. — The  apparatus  Fig.  8,  is  enclosed  in 
a  case  to  permit  of  transportation  from  place  to  place; 
furthermore,  the  measuring-tube  is  jacketed  with 
water  to  prevent  changes  of  temperature  affecting  the 
gas-volume.  The  apparatus  consists  essentially  of 
the  levelling-bottle  A,  the  burette  B,  the  pipettes 
P't  P",  P'",  and  the  connecting  tube  T. 

ii 


12  GAS  AND   FU^L   ANALYSIS. 

Manipulation. —  The  reagents  in  the  pipettes  should 
be  adjusted  in  the  capillary  tubes  to  a  point  on  the 
stem  about  midway  between  the  top  of  the  pipette 
and  the  rubber  connector.  This  is  effected  by  open- 
ing wide  the  pinchcock  upon  the  connector,  the 


FIG.  8. — ORSAT'S  GAS  APPARATUS. 

bottle  being  on  the  table,  and  very  gradually  lower- 
ing the  bottle  until  the  reagent  is  brought  to  the  point 
above  indicated.  Six  inches  of  the  tubing  used  corre- 
spond to  but  o.i  cc.,  so  that  an  error  of  half  an  inch 
in  adjustment  of  the  reagent  is  without  influence 
upon  the  accuracy  of  the  result.  The  reagents  having 
been  thus  adjusted,  the  burette  and  connecting  tube 
are  completely  filled  with  water  by  opening  d  and 
raising  the  levelling-bottle.  The  apparatus  is  now 


ANALYSIS   OF  CHIMNEY-GASES.  13 

ready  to  receive  a  sample  of  gas  (or  air  for  prac- 
tice). In  case  a  flue-gas  is  to  be  analyzed  d  is  con- 
nected with  z,  Fig.  2,  A  lowered  and  about  102  cc. 
of  the  gas  forced  over  by  opening  h;  or  d  may 
be  connected  with  aT  joint  in  the  gas-stream;  the 
burette  after  filling  is  allowed  to  drain  one  minute  by 
the  sand-glass,  c  snapped  upon  its  rubber  tube,  and 
the  bottle  A  raised  to  the  top  of  the  apparatus.  By 
gradually  opening  c  the  water  is  allowed  to  run  into 
the  burette  until  the  lower  meniscus  stands  upon  the 
100  or  o  mark  (according  to  the  graduation  of  the 
apparatus).  The  gas  taken  is  thus  compressed  into 
the  space  occupied  by  100  cc.,  and  by  opening  d  the 
excess  escapes.  Open  c  and  bring  the  level  of  the 
water  in  the  bottle  to  the  same  level  as  the  water  in  the 
burette  and  take  the  reading,  which  should  be  100  cc. 
Special  attention  is  called  to  this  method  of  reading: 
if  the  bottle  be  raised,  the  gas  is  compressed;  if 
lowered,  it  is  expanded. 

Determination  of  Carbon  Dioxide. — The  gas  to  be 
analyzed  in  invariably  passed  first  into  pipette  P',  con- 
taining potassium  hydrate  for  the  absorption  of  carbon 
dioxide,  by  opening  e  and  raising^.  The  gas  dis- 
places the  reagent  in  the  front  part  of  the  pipette, 
laying  bare  the  tubes  contained  in  it,  which  being 
covered  with  the  reagent  present  a  large  absorptive 
surface  to  the  gas;  the  reagent  moves  into  the  rear 
arm  of  the  pipette,  displacing  the  air  over  it  into  the 
flexible  rubber  bag  which  prevents  its  diffusion  into 
the  air.  The  gas  is  forced  in  and  out  of  the  pipette 
by  raising  and  lowering^,  the  reagent  finally  brought 
approximately  to  its  initial  point  on  the  stem  of  the 


OF  THE 
UNI  VF.T3  OTT^rr- 


14  GAS  AND    FUEL    ANALYSIS. 

pipette,  the  burette  allowed  to  drain  one  minute,  and 
the  reading  taken.  The  difference  between  this  and 
the  initial  reading  represents  the  cubic  centimeters  of 
carbon  dioxide  present  in  the  gas.  To  be  certain  that 
all  the  carbon  dioxide  is  removed,  the  gas  should  be 
passed  a  second  time  into  P'  and  the  reading  taken 
as  before;  these  readings  should  agree  within  o.  I  per 
cent. 

Determination  of  Oxygen. — The  residue  from  the 
absorption  of  carbon  dioxide  is  passed  into  the  second 
pipette,  P",  containing  an  alkaline  solution  of  potas- 
sium pyrogallate,  until  no  further  absorption  will  take 
place.  The  difference  between  the  reading  obtained 
and  that  after  the  absorption  of  carbon  dioxide,  repre- 
sents the  number  of  cubic  centimeters  of  oxygen 
present. 

Determination  of  Carbonic  Oxide. — The  residue 
from  the  absorption  of  oxygen  is  passed  into  the  third 
pipette,  P'"t  containing  cuprous  chloride,  until  no 
further  absorption  takes  place;  that  is,  in  this  case 
until  readings  agreeing  exactly  (not  merely  to  o.  i)  are 
obtained.  The  difference  between  the  reading  thus 
obtained  and  that  after  the  absorption  of  oxygen, 
represents  the  number  of  cubic  centimeters  of  carbonic 
oxide  present. 

Determination  of  Hydrocarbons.  —  The  residue 
left  after  all  absorptions  have  been  made  may  consist, 
in  addition  to  nitrogen,  the  principal  constituent,  of 
hydrocarbons  and  hydrogen.  Their  determination  is 
difficult  for  the  inexperienced,  and,  if  desired,  a  sample 
of  the  flue-gas  should  be  taken,  leaving  as  little  water 


ANALYSIS   OF  CHIMNEY-GASES.  15 

in  the  apparatus  as  possible,  and  sent  to  a  competent 
chemist  for  analysis. 

Accuracy. — The  apparatus  gives  results  accurate  to 
0.2  of  one  per  cent. 

Time  Required. — About  twenty  minutes  are  re- 
quired for  an  analysis ;  two  may  be  made  in  twenty  five 
minutes,  using  two  apparatus. 

Notes. — The  method  of  adjusting  the  reagents  is  the 
only  one  which  has  been  found  satisfactory:  if  the 
bottle  be  placed  at  a  lower  level  and  an  attempt  made 
to  shut  the  pinchcock  c  upon  the  connector  at  the 
proper  time,  it  will  almost  invariably  result  in  failure. 

The  process  of  obtaining  100  cc.  of  gas  is  exactly 
analagous  to  filling  a  measure  heaping  full  of  grain  and 
striking  off  the  excess  with  a  straight-edge;  it  saves 
arithmetical  work,  as  cubic  centimeters  read  off  repre- 
sent percent  directly. 

It  often  happens  when  e  is  opened,  c  being  closed, 
that  the  reagent  in  P'  drops,  due  not  to  a  leak  as  is 
usually  supposed,  but  to  the  weight  of  the  column  of 
the  reagent  expanding  the  gas. 

The  object  of  the  rubber  bags  is  to  prevent  the 
access  of  air  to  the  reagents,  those  in  P"  and  P"f 
absorbing  oxygen  with  great  avidity,  and  hence  if 
freely  exposed  to  the  air  would  soon  become  useless. 

Carbon  dioxide  is  always  the  first  gas  to  be  removed 
from  a  gaseous  mixture.  In  the  case  of  air  the  per- 
centage present  is  so  small,  0.08  to  o.  I,  as  scarcely  to 
be  seen  with  this  apparatus.  It  is  important  to  use 
the  reagents  in  the  order  given ;  if  by  mistake  the  gas 
be  passed  into  the  second  pipette,  it  will  absorb  not 
only  oxygen,  for  which  it  is  intended,  but  also  carbon 


l6  GAS  AND   FUEL   ANALYSIS. 

dioxide;  similarly  if  the  gas  be  passed  into  the  third 
pipette,  it  will  absorb  not  only  carbonic  oxide,  but 
also  oxygen  as  well. 

The  use  of  pinchcocks  and  rubber  tubes,  original 
with  the  author,  although  recommended  by  Naef,*  is 
considered  by  Fischer,  f  to  be  inaccurate.  The  ex- 
perience of  the  author,  however,  does  not  support 
this  assertion,  as  they  have  been  found  to  be  fully 
as  accurate  as  glass  stopcocks,  and  very  much  less 
troublesome  and  expensive. 

In  case  any  potassium  hydrate  or  pyrogallate  be 
sucked  over  into  the  tube  T or  water  in  A,  the  analysis 
is  not  spoiled,  but  may  be  proceeded  with  by  connect- 
ing on  water  at  d,  opening  this  cock,  and  allowing  the 
water  to  wash  the  tubes  out  thoroughly.  The  addi- 
tion of  a  little  hydrochloric  acid  to  the  water  in  the 
bottle  A  will  neutralize  the  hydrate  or  pyrogallate,  and 
the  washing  may  be  postponed  until  convenient. 

After  each  analysis  the  number  of  cubic  centimeters 
of  oxygen  and  carbonic  oxide  should  be  set  down  upon 
the  ground-glass  slip  provided  for  the  purpose.  By 
adding  these  numbers  and  subtracting  their  sum  from 
the  absorption  capacity  (see  Reagents)  of  each  reagent, 
the  condition  of  the  apparatus  is  known  at  any  time, 
and  the  reagent  can  be  renewed  in  season  to  prevent 
incorrect  analyses. 

BUNTE   APPARATUS. 

Description. — The  apparatus  Fig.  9  consists  of  a 
burette — bulbed  to  avoid  extreme  length — provided 

*  Wagner's  Jahresb.  1885,  p.  423. 

f  Technologic  d.  Brennstoffe,  foot  note  p.  295, 


ANALYSIS  OF  CHIMNEY-GASES.  17 

at  the  top  with  a  funnel  F  and  three-way  cock/,  and 
a  cock  /  at  the  bottom.  These  stopcocks  are  best 
of  the  Greiner  and  Friedrichs  obliquely  bored  form. 
The  burette  is  supported  upon  a  retort-  (=• 

stand  with  a  spring  clamp. 

A  "suction-bottle  "  5,  an  8-oz.  wide- 
mouthed  bottle,  fitted  similarly  to  a 
wash-bottle,  except  that  the  delivery- 
tube  is  straight  and  is  fitted  with  a 
four-inch  piece  of  J-inch  black  rubber 
tubing,  serves  to  withdraw  the  re- 
agents and  water  when  necessary.  A 
reservoir  to  contain  water  at  the  tem- 
perature of  the  room,  fitted  with  along 
rubber  tube,  should  be  provided  for 
washing  out  the  reagents  and  filling 
the  burette. 

Manipulation.  —  Before  using  the 
apparatus,  the  keys  of  the  stopcocks 
should  be  taken  out,  wiped  dry,  to- 
gether with  their  seats,  and  sparingly 
smeared  with  vaseline  or  a  mixture  of 
vaseline  and  tallow  and  replaced.  The  FIG.  9.— BUNTE'S 
completeness  of  the  lubrication  can  be  GAS  AppARATUS- 
judged  by  the  transparency  of  the  joint,  a  thoroughly 
lubricated  joint  showing  no  ground  glass.  The 
burette  is  filled  with  water  by  attaching  the  rubber 
tube  to  the  tip  at  /  and  opening  the  stopcocks  at  the 
top  and  bottom ;  /  is  connected  with  the  source  whence 
the  gas  is  to  be  taken,  turned  to  communicate  with 
the  burette  and  opened,  about  102  cc.  of  gas  allowed 
to  run  in,  and/ and  /closed. 


1 8  GAS  AND    FUEL  ANALYSIS. 

The  cup  F  is  filled  with  water  to  the  2$-cc.  mark,/ 
turned  to  establish  communication  between  it  and  the 
burette,  the  burette  allowed  to  drain  one  minute  by 
the  sand-glass,  and  the  reading  taken,  the  cup  being 
refilled  to  the  mark  if  necessary.  The  readings  are 
thus  taken  under  the  same  pressure  each  time,  i.e., 
this  column  of  water  plus  the  height  of  the  barometer; 
and  as  the  latter  is  practically  constant  during  the 
analysis,  no  correction  need  be  applied,  it  being  within 
the  limits  of  error. 

Determination  of  Carbon  Dioxide. — The  "  suc- 
tion-bottle "  is  connected  with  the  tip  of  the  burette, 
/  opened,  and  the  water  carefully  sucked  out  nearly  to 
/.  The  bottle  is  now  disconnected,  the  burette  dis- 
mounted from  its  clamp,  using  the  cup  as  a  handle, 
and  the  25  cc.  of  water  turned  out.  The  tip  is 
immersed  under  potassium  hydrate  contained  in  the 
No.  3  porcelain  dish,  and  the  cock  /  opened,  then 
closed,  and  the  tip  wiped  clean  with  a  piece  of  cloth. 
The  burette  is  now  shaken,  holding  it  by  the  tip  and 
the  cup,  the  thumbs  resting  upon  /  and  /;  more 
reagent  is  introduced,  the  absorption  of  the  gas  caus- 
ing a  diminished  pressure,  and  the  operation  repeated 
until  no  change  takes  place.  The  cup  is  now  filled 
with  water,  j  opened,  and  the  leagent  completely 
washed  out  into  an  ordinary  tumbler  placed  beneath 
the  burette.  Four  times 'filling  of  F  should  be  suffi- 
cient for  this  purpose.  The  cup  is  now  filled  to  the 
25-cc.  mark,  j  opened,  and  the  reading  taken  as 
before. 

The  difference  between  this  reading  and  the  initial 
represents  the  number  of  cubic  centimeters  of  carbon 


ANALYSIS   OF  CHIMNEY-GASES.  1 9 

dioxide;  this  divided  by  the  volume  of  the  gas  taken 
gives  the  per  cent  of  this  constituent. 

Determination  of  Oxygen. — The  water  is  again 
sucked  out,  and  potassium  pyrogallate  solution  intro- 
duced, similarly  to  potassium  hydrate;  this  is  dis- 
placed by  water,  and  the  reading  taken  as  before. 
The  difference  between  this  and  the  last  reading  is  the 
volume  of  oxygen  present. 

Determination  of  Carbonic  Oxide. — The  water  is 
removed  for  a  third  time,  and  acid  cuprous  chloride 
solution  introduced  and  the  absorption  made  as  before ; 
this  is  washed  out,  first  with  water  containing  a  little 
hydrochloric  acid  to  dissolve  the  white  cuprous  chlo- 
ride which  is  precipitated  by  the  addition  of  water, 
and  finally  with  pure  water,  and  the  reading  taken  as 
before.  The  difference  between  this  and  the  preced- 
ing gives  the  volume  of  carbonic  oxide  present. 

Notes. — Especial  care  should  be  taken  not  to  grasp 
the  burette  by  the  bulb,  as  this  warms  the  gas  and 
renders  the  readings  inaccurate.  The  stopcocks  can 
conveniently  be  kept  in  the  burette  by  elastic  bands 
of  suitable  size.  When  the  apparatus  is  put  away  for 
any  considerable  time,  a  piece  of  paper  should  be 
inserted  between  the  key  and  socket  of  each  stopcock 
to  prevent  the  former  from  sticking  fast.  To  ascer- 
tain when  the  absorption  is  complete,  the  burette  is 
mounted  in  its  clamp  and  allowed  to  drain  until  the 
meniscus  is  stationary,  the  dish  containing  the  reagent 
raised  until  the  tip  is  covered,  /opened,  and  any  change 
in  level  noted.  If  the  meniscus  rises,  the  absorption 
is  incomplete  and  must  be  continued;  if  it  remains 
stationary  or  falls,  the  absorption  may  be  regarded  as 


20  GAS  AND   FUEL  ANALYSIS. 

finished.  In  case  the  grease  from  the  stopcocks 
becomes  troublesome  inside  the  burette,  it  may  be 
removed  by  dissolving  it  in  chloroform  and  washing 
out  with  alcohol  and  then  with  water.  The  object  in 
sucking  the  water  not  quite  down  to  /,  thus  leaving  a 
little  water  in  the  burette,  is  to  discover  if  /  leaks,  the 
air  rushing  in  causes  bubbles. 

The  object  in  washing  out  each  reagent  and  taking 
all  readings  over  water  is  to  obviate  corrections  for 
the  tension  of  aqueous  vapor  over  potassium  hydrate, 
hydrochloric  acid,  or  any  of  the  reagents  which  might 
be  employed.  The  tension  of  aqueous  vapor  over 
seven  per  cent  caustic  soda  is  less  than  over  water. 

Accuracy  and  Time  Required. — The  apparatus  is 
rather  difficult  to  manipulate,  but  fairly  rapid — about 
twenty-five  minutes  being  required  for  an  analysis — 
and  accurate  to  one  tenth  of  one  per  cent. 

ELLIOTT   APPARATUS. 

Description. — The  apparatus  Fig.  10  consists  of  a 
burette  holding  100  cc.  graduated  in  tenths  of  a  cubic 
centimeter  and  bulbed  like  the  Bunte  apparatus — the 
bulb  holding  about  30  cc.  ;  it  is  connected  with  a 
levelling-bottle  similar  to  the  Orsat  apparatus.  The 
top  of  the  burette  ends  in  a  capillary  stopcock,  the 
stem  of  which  is  ground  square  to  admit  of  close  con- 
nection with  the  " laboratory  vessel,"  an  ungraduated 
tube  similar  to  the  burette,  except  of  125  cc.  capacity. 
The  top  of  this  "vessel  "  is  also  closed  with  a  capil- 
lary stopcock,  carrying  by  a  ground-glass  joint  a 
thistle-tube  F,  for  the  introduction  of  the  reagents. 
The  lower  end  of  this  "  vessel  "  is  closed  bv  a  rubber 


ANALYSIS  OF  CHIMNEY-GASES. 


21 


stopper  carrying  a  three-way  cock  <?,  and  connected 
with  a  levelling-bottle  D.  The 
burette  and  vessel  are  held  upon  a 
block  of  wood — supported  by  a  ring 
stand — by  fine  copper  wire  tight- 
ened by  violin  keys. 

Manipulation. — The  ground-glass 
joints  are  lubricated  as  in  the  Bunte 
apparatus.  The  levelling  bottles  are 
filled  with  water,  the  stopcocks 
opened,  and  the  bottles  raised  until 
the  water  flows  through  the  stop- 
cocks m  and  n.  m  is  connected 
with  the  source  whence  the  gas  to 
be  analyzed  is  to  be  taken,  n  closed, 
D  lowered  and  rather  more  than  100 
cc.  drawn  in,  and  m  closed,  n  is 
opened,  D  raised  and  E  lowered, 
nearly  100  cc.  of  gas  introduced, 
and  n  closed;  by  opening  m  and 
raising  D  the  remainder  of  the  gas 
is  allowed  to  escape,  the  tubes  being 
filled  with  water  and  m  closed,  n  is 
opened  and  the  water  brought  to 
the  reference-mark;  the  burette  is 
allowed  to  drain  one  minute,  the 
level  of  the  water  in  E  is  brought 
to  the  same  level  as  in  the  burette, 


and  the  reading  taken. 


FIG.  10. — ELLIOTT 
GAS  APPARATUS. 


Determination  of  Carbon  Dioxide — By  raising  E, 
opening  n,  and  lowering  D,  the  gas  is  passed  over  into 
the  laboratory  vessel;  F  is  filled  within  half  an  inch 


22  GAS  AND   FUEL  ANALYSIS. 

of  the  top  with  potassium  hydrate,  o  closed,  ;//  opened, 
and  the  reagent  allowed  to  slowly  trickle  in.  A  No.  3 
evaporating-dish  is  placed  under  o1  and  this  turned  to 
allow  the  liquid  in  the  laboratory  vessel  to  run  into 
the  dish.  At  first  this  is  mainly  water,  and  may  be 
thrown  away;  later  it  becomes  diluted  reagent  and 
may  be  returned  to  the  thistle-tube.  When  the 
depth  of  the  reagent  in  the  thistle-tube  has  lowered 
to  half  an  inch,  it  should  be  refilled  either  with  fresh 
or  the  diluted  reagent  and  allowed  to  run  in  until  the 
absorption  is  judged  to  be  complete,  and  the  gas 
passed  back  into  the  burette  for  measurement.  To 
this  end  close  o  and  then  m,  raise  E,  open  ;/,  and 
force  some  pure  water  into  the  laboratory  vessel,  thus 
rinsing  out  the  capillary  tube.  Now  raise  D  and  lower 
E,  shutting  n  when  the  liquid  has  arrived  at  the  refer- 
ence-mark. The  burette  is  allowed  to  drain  a  minute, 
the  level  of  the  water  in  the  bottle  E  brought  to  the 
same  level  as  the  water  in  the  burette,  and  the  reading 
taken. 

Determination  of  Oxygen. — The  manipulation  is 
the  same  as  in  the  preceding  determination,  potassium 
pyrogallate  being  substituted  for  potassium  hydrate; 
the  apparatus  requiring  no  washing  out. 

Determination  of  Carbonic  Oxide. — The  labora- 
tory vessel,  thistle-tube,  and  bottle  if  necessary,  are 
washed  free  from  potassium  pyrogallate  and  the 
absorption  made  with  acid  cuprous  chloride  similarly 
to  the  determination  of  carbon  dioxide.  The  white 
precipitate  of  cuprous  chloride  may  be  dissolved  by 
hydrochloric  acid. 


ANALYSIS   OF  CHIMNEY-GASES.  2$ 

Accuracy  and  Time  Required. — The  apparatus  is 
as  accurate  for  absorptions  as  that  of  Orsat;  it  is 
stated  to  be  much  more  rapid — a  claim  which  the  writer 
cannot  substantiate.  It  is  not  as  portable,  is  more 
fragile,  and  more  troublesome  to  manipulate,  and  as 
the  burette  is  not  jacketed  it  is  liable  to  be  affected 
by  changes  of  temperature. 

Notes. — In  case  at  any  time  it  is  desired  to  stop 
the  influx  of  reagent,  o  should  be  closed  first  and 
then  ;«;  the  reason  being  that  the  absorption  may 
be  so  rapid  as  to  suck  air  in  through  o,  m  being 
closed. 

The  stopcock  should  be  so  adjusted  as  to  cause  the 
reagent  to  spread  itself  as  completely  as  possible  over 
the  sides  of  the  burette. 

By  the  addition  of  an  explosion-tube  it  is  used  for 
the  analysis  of  illuminating-gas,*  bromine  being  used 
to  absorb  the  "  illuminants."  Winkler  f  has  shown 
that  this  absorption  is  incomplete,  and  Hempel  J  that 
explosions  of  hydrocarbons  made  over  water  are  in- 
accurate, so  that  the  apparatus  can  be  depended  upon 
to  give  results  upon  methane  and  hydrogen  only  within 
about  two  per  cent. 

*  Mackintosh,  Am.  Chem.  Jour.  9,  294. 
f  Zeitsch.  f.  Anal.  Chem.  28,  286. 
%  Gasanalytische  Methoden,  p.  102. 


CHAPTER    III. 
MEASUREMENT   OF   TEMPERATURE. 

IN  the  majority  of  cases,  the  ordinary  mercurial 
thermometer  will  serve  to  determine  the  temperature 
of  the  chimney-gases.  It  should  not  be  inserted  naked 
into  the  flue,  but  be  protected  by  a  bath  of  cylinder, 
or  raw  linseed  oil,  contained  in  a  brass  or  iron  tube. 
These  tubes  may  be  half  an  inch  inside  diameter  and 
two  to  three  feet  in  length.  Temperatures  as  high  as 
625°  C.  have  been  observed  in  chimneys;  this  lasts  of 
course  but  for  a  moment,  but  would  be  sufficient  to 
burst  the  unprotected  thermometer. 

For  the  observation  of  higher  temperatures,  recourse 
must  be  had  to  the  "  high-temperature  thermom- 
eters," rilled  with  carbon  dioxide  under  a  pressure  of 
about  one  hundred  pounds,  giving  readings  to  550°  C.* 
These  may  be  obtained  of  the  dealers  in  chemical 
apparatus;  some  require  no  bath,  being  provided 
with  a  mercury-bath  carefully  contained  in  a  steel 
tube,  and  the  whole  enclosed  in  a  bronze  tube.f 

*  Those  made  by  W.  Apel,  Gottingen,  Germany,  are  about  three 
feet  long,  the  scale  occupying  about  one  foot,  thus  avoiding  the 
necessity  of  withdrawing  the  thermometer  from  the  bath  for 
reading. 

f  Those  made  by  the  Hohmann  and  Maurer  Co.,  Brooklyn, 
N.  Y. 

24 


((UNIVERSITY  J 
MEASUREMENT  OF\£MJPE£^TUREJf         2$ 


These  thermometers  should  be  tested  from  time  to 
time  either  by  comparison  with  a  standard  or  by  inser- 
tion in  various  baths  of  a  definite  temperature.  Some 
of  the  substances  used  for  these  baths  are:  water,  boil- 
ing-point 1 00°;  naphthalene,  Bpt.  219°;  benzophenon, 
Bpt.  306°;  and  sulphur,*  Bpt.  445°.  Care  should  be 
taken  that  the  bulb  of  the  thermometer  does  not  dip 
into  the  melted  substance,  but  only  into  the  vapor, 
and  that  the  stem  exposure  be  as  nearly  as  possible 
that  in  actual  use. 

For  the  measurement  of  temperatures  beyond  the 
range  of  these  thermometers  the  Le  Chatelier  thermo- 
electric pyrometer  may  be  used.  This  consists  of  a 
couple  formed  by  the  junction  of  a  platinum  and 
platinum-  io#  rhodium  wire,  passing  through  fire-clay 
tubes  in  a  porcelain  or  iron  envelope  and  connected 
with  a  galvanometer.  The  hotter  the  junction  is 
heated  the  greater  the  current  and  the  galvanometer 
deflection;  this  latter  is  determined  for  several  points, 
naphthalene,  sulphur,  and  copper,  Mpt.  1095°  C.,  or 
even  platinum,  1760°  C.,  and  a  plot  made  with  gal- 
vanometer-readings as  abscissae  and  temperatures  as 
ordinates.  From  this  the  temperature  corresponding 
to  any  deflection  is  readily  obtained. 

The  exact  description  of  the  instrument  and  details 
of  calibration  are,  however,  beyond  the  scope  of  this 
work,  and  the  student  is  referred  for  these  to  articles 
by  Le  Chatelier,  Societe  Technique  de  1'Industrie  du 
Gaz,  1890,  abstracted  in  Jour.  Soc.  Chem.  Industry, 

*  In  testing  the  H.  &  M.  thermometers  in  sulphur-vapor,  the 
bronze  tube  should  be  prevented  from  corrosion  by  the  vapor  by 
a  glass  envelope. 


26 


GAS  AND    FUEL   ANALYSIS. 


9,    326,   and  Holman,  Proc.  Am.  Academy,  1895,  p. 

234. 

An  error  of  5°  in  the  reading  of  the  thermometer 
affects  the  final  result  by  about  20  calories. 

In  case  neither  of  these  methods  be  available  nor 


FIG.  n. — MELTING-POINT  BOXES. 

applicable,  use  may  be  made  of  the  melting-points 
of  certain  metals  or  salts  contained  in  small  cast-iron 
boxes,  Fig.  n.  The  melting-points  of  certain  metals 
and  salts  are  given  in  Table  VII. 


CHAPTER    IV. 
CALCULATIONS. 

As  has  been  already  stated  in*the  Introduction,  the 
object  of  analyzing  the  flue-gases  is  to  ascertain,  first, 
the  completeness  of  the  combustion,  especially  the 
amount  of  air  which  has  been  used  or  the  li  pounds  of 
air  per  pound  of  coal,"  and  second,  the  amount  of 
heat  passing  up  chimney. 

i.  To  Ascertain  the  Number  of  Pounds  of  Air 
per  Pound  of  Coal. — A  furnace-gas  gives  11.5$  COa, 
7.4$  O,  0.9$  CO,  and  80.2$  N.  Data:  atomic  weights, 
O  —  16,  C  =  12;  weight  liter  CO2  =  1.966  grs.,  of 
O,  1.43  grs.,  of  CO,  1.251  grs.  Find  the  number  of 
grams  of  each  constituent  in  100  liters  of  the  furnace- 
gas,  and  from  this  the  weight  of  carbon  and  weight  of 
oxygen.  11.5  (liters  CO3)  X  1.97  (wt.  liter  CO2)  = 

22.66  grms.  CO,;  now  —  ^Qy)   of  this  is  oxygen  = 

16.41  grms.,  6.25  grms.  is  carbon.  The  weight  of 
free  oxygen  is  7.4  X  1-43  =  10.58  grms.  The  weight 
of  carbon  and  oxygen  in  the  carbonic  oxide  is  0.9  X 

1.25=  1. 1 2  grms.  CO.     Now  -«(™ Vs  oxygen  or  0.64 

grm.,  and  0.48  grm.  is  carbon.  There  are  then  pres- 
ent in  100  liters  of  the  gas  27.63  grms.  oxygen  and 
6.73  grms.  carbon;  corresponding  to  119. 6  grms.  air 

27 


28  GAS  AND   FUEL   ANALYSIS. 

to   6.73    grms.    carbon,    air   being   23.1$   oxygen    by 

grms.  )  grm.  ) 

weight;   or   17.77   „          |  air  per  .          j  carbon.       If 

the  coal  be  83$  carbon,  this  figure  must  be  diminished 
accordingly,  giving  in  this  case  14.75  IDS-  air  per  Ib. 
of  coal.  Theory  requires  11.54  Ibs.  air  per  Ib.  of  car- 
bon, but  in  practice  the  best  results  are  obtained  by 
increasing  this  from  50$  to  100$.* 

2.  To  Ascertain  the  Quantity  of  Heat  Passing 
up  Chimney — Determine  the  volume  of  gas  generated 
from  one  kilo  of  coal  when  burned  so  as  to  produce 
the  gas  the  analysis  of  which  has  just  been  made 
according  to  the  directions  given.  The  chemical 
analysis  of  the  coal  is  as  follows:  moisture  1.5$, 
sulphur  1.2$,  carbon  83$,  hydrogen  2.5$,  ash  11.4$, 
oxygen  and  nitrogen  (by  difference)  0.4$.  Then 
there  are  in  one  kilo  of  coal  830  grms.  carbon,  of 
this  suppose  but  800  to  be  burned,  the  remaining  30 
grms.  going  into  the  ash:  of  the  800  grms.  625/673 
or  743  grms.  produced  carbon  dioxide,  and  48/673 
or  57  grms.  produced  carbonic  oxide.  From  6.25 
grms.  carbon  were  produced  11.5  liters  carbon  di- 
oxide in  the  problem  in  I  ;  hence  743  grms.  would 
furnish  1367  liters.  6.25  :  743  ::  1 1.5  \y.  y  —  1367. 
Similarly  57  grms.  carbon  would  furnish  107.4  liters 
carbonic  oxide.  0.48  :  57: :  1. 12  :  z.  2=107.4.  The 
volume  of  oxygen  can  be  found  by  the  proportion 
11.5  ($  CO2) :  7.4  (#O) : :  1 367  :  x.  x  —  880  liters.  In 
the  same  manner  the  nitrogen  is  found  to  be  9535 
liters.  1 1.5  :  80.2  ::  1367:  u.  »  =  9535-  One  kilo  of 
coal  under  these  conditions  furnishes  1.367  cu.  meter 

*Scheurer-Kestner,  Jour.  Soc.  Chem.  Industry,  7,  616. 


CALCULATIONS.  2Q 

carbon    dioxide,    0.107    c.   m.  carbonic   oxide,   0.880 
c.  in.  oxygen,  and  9.535  c.  m.  nitrogen. 

The  quantity  of  heat  carried  off  by  each  gas  is  its 
rise  of  temperature  X  its  weight  X  its  specific  heat, 
The  specific  heats  of  the  various  gases  are  shown  in 
the  table  below,  and  for  facility  in  calculation,  a  column 
is  given  obtained  by  multiplying  the  weight  by  the 
specific  heat;  multiplying  the  volumes  obtained  in  the 
previous  calculation  by  the  numbers  in  this  column 
and  by  the  rise  in  temperature  gives  the  number  of 
calories  (C)  that  each  gas  carries  away. 

TABLE    OF    SPECIFIC    HEATS    OF   VARIOUS    GASES.* 
S,  Hea, 


. 

Carbon  dioxide  (io°-35o°).  0.234  1.98  0.463  9.6656 

"        monoxide  .........  0.245  1.26  0.308  9.4886 

Oxygen  ..................  0.217  1-43  0.311  9.4928 

Nitrogen.  ,«  ..............  0.244  1.26  0.306  9.4857 

Aqueous  vapor  ...........  0.480  0.80  0.387  9-5877 

In  the  test  the  average  temperature  of  the  escaping 
gases  was  275°  C.  ;  that  of  the  air  entering  the  grate 
was  25°  C.,  a  rise  of  temperature  of  250°  C.  As 
shown  by  the  wet-and-dry-bulb  thermometer,  the  air 
was  50  per  cent  saturated  with  moisture. 

The  calculation  of  the  heat  carried  away  is  then  for: 

Cu.  M.  C. 

Carbon  dioxide  ...........     1-367  X  250  X  0.463  =  158.2 

Carbonic  oxide  ...........     o.  107  X    "    X  0.308  =      8.2 

Oxygen  ..................     o.SSoX    "    X  o  311  =    68.4 

Nitrogen  .................     9-535  X    "    X  0.306  =  729.3 

Total  ..............   11.989  964.1 

*  Fischer,  Tech.  d.  Brennstoffe,  p.  267. 


30  GAS  AND    FUEL   ANALYSIS. 

There  is,  however,  another  gas  passing  up  chimney 
of  which  we  have  taken  no  cognizance,  namely,  water- 
vapor;  this  comes  from  the  moisture  in  the  coal,  from 
the  combustion  of  hydrogen  in  the  coal,  and  from  the 
air  entering  the  grate;  its  volume  is  calculated  as 
follows: 

The  moisture  in  the  coal  as  found  by  chemical 
analysis  was  1.5$  —  0.015  kg.;  the  hydrogen  in  the 
coal  was  2.5$  =  0.025  kg.  The  amount  of  water  this 
forms  when  burned  is  nine  times  its  weight,  0.025  kg. 
X  9  =  0.225  kg.  The  moisture  in  the  air  entering  the 
grate  would  be,  if  completely  saturated,  22.9  grams 
per  cubic  meter,  as  shown  by  Table  I ;  it  was,  how- 
ever, but  50$  saturated.  The  quantity  is  then,  the 
volume  of  air  used  per  kilogram  of  coal  X  moisture 
contained  in  it,  or  1 1.989  X  22.9  X  0.50  —  o,  137  kg. 
The  weight  of  aqueous  vapor  passing  up  chimney  per 
kilogram  of  coal  is  0.015-1-0.225-1-0.137  =  0.377 
kg. ;  the  quantity  of  heat  that  this  carries-  off  is  0.377 
X  250  X  0.480  =  45.2  C.  The  total  quantity  of  heat 
passing  up  chimney  is  then  1009.3  C.  The  heat  of 
combustion  of  this  coal  as  found  by  Mahler's  calori- 
metric  bomb  was  7220  C. ;  hence  the  percentage  of 
heat  carried  off  is  1009/7220  =  14$. 

The  preceding  calculations  though  correct  are 
tedious,  so  much  so,  as  to  almost  preclude  their  use 
for  an  hourly  observation  of  the  firing.  They  should 
be  employed,  however,  in  making  the  final  calculation 
of  a  boiler-test,  using  the  averages  obtained. 

In  rapid  work  the  following  formula  will  be  found 
more  applicable:  Let  o  and  n  represent  the  percent- 
ages of  oxygen  and  nitrogen  found  in  the  chimney- 


CALCULA  TIONS.  3 1 

gas;   then  the   ratio  of  the  air  actually  used  to   that 
theoretically  necessary  is  expressed  by  the  formula 

21 


--fir0! 

Applying    it    in  the    case    of    the    flue-gas    given,   it 
becomes 

21  21 


(79  X  7-4\        13-7 
21  ~\     80.2 


=  1.533  ratio. 


Multiplying  this  by  11.54,  the  theoretical  number  of 
pounds  of  air  per  pound  of  carbon,  we  obtain  17.69  as 
against  17.77  on  Page  2%- 

Lunge  *  has  given  a  shorter  method  for  the  deter- 
mination of  the  quantity  of  heat  passing  up  chim- 
ney, and  one  which  does  not  involve  the  analysis  of 
the  coal. 

One  kilogram  of  pure  carbon  yields,  when  burned, 
1.854  cubic  meters  of  carbon  dioxide  under  standard 
conditions  and  evolves  8080  calories.  By  the  analysis 
of  the  gases  we  obtain  the  percentages  of  carbon 
dioxide,  oxygen,  and  nitrogen.  Let  k  —  per  cent  of 
carbon  dioxide,  then  100  —  k  represents  the  per  cent 
of  nitrogen  and  oxygen  together.  Let  1.854  cu.  m. 
represent  this  per  cent  of  carbon  dioxide,  then  xy  the 
volume  of  the  nitrogen  and  oxygen,  may  be  found  by 
the  proportion  1.854:  k\  :  x\  (100  —  k). 


*  Zeit.  f.  angewandte  Chemie,  1889,  240. 


32  GAS  AND   FUEL  ANALYSIS. 

Let  /  be  the  temperature  of  the  air  entering  the 
grate,  and  /'  that  of  the  gases  in  the  chimney;  then 
t'  —  t  represents  the  rise  of  temperature.  Let  c  repre- 
sent the  specific  heat  of  a  cubic  meter  of  carbon  dioxide 
—  0.46,  p.  29,  and  c'  that  of  a  cubic  meter  of  ni- 
trogen =  0.31.  Then  the  loss  of  heat  is  represented 
by  the  formula 

i.8S4(f  -  t)c  +  1.854 
The  percentage  of  heat  lost  is  then 

Loss  of  heat  X  100 
8080  ' 

Substituting  in  this  formula  for  k,  1  1.5,  t'  —  t,  250°, 
we  obtain 

Loss  of  heat  = 

(i.854)(25o)(.46)  +  i.854(^|)(25o)(o.3i)=  1319. 
1319  X  ioo 

~ 


loss  of  heat  as  against  14$  on  page  30. 

This  formula  gives  results  which  are  usually  2  to  2j 
per  cent  too  high. 

Determination  of  Loss  Due  to  Formation  of  Car- 
bonic Oxide.  —  On  page  28  we  see  that  57  grams  of 
carbon  burned  to  carbonic  oxide;  for  every  gram  of 
carbon  burned  to  carbonic  oxide  there  is  a  loss  of 
5.66  C.,  in  this  case  a  loss  of  323  C.  The  heating 
value  of  the  coal  is  7220  C.,  hence  the  loss  is  4.5  per 
cent. 


CA  L  CULA  TIOKS.  3  3 

Determination  of  the  Loss  Due  to  Unconsumed 
Fuel. — The  per  cent  of  carbon  in  the  ash  being 
determined  by  chemical  analysis,  and  the  weight  of 
the  ash  being  known,  the  weight  of  the  unburned  car- 
bon can  be  determined.  This  can  be  then  calculated 
as  coal,  which  divided  by  the  weight  of  coal  fired 
gives  the  loss  due  to  this  source.  This  loss  varies 
from  5  to  7  per  cent.  This  should  be  taken  cogni- 
zance of  in  calculating  the  volume  of  flue-gases  formed 
from  one  kilogram  of  coal. 


CHAPTER  V. 

REAGENTS  AND  ARRANGEMENT  OF  THE 
LABORATORY. 

THE  reagents  used  in  gas-analysis  are  comparatively 
few  and  easily  prepared. 

Hydrochloric  Acid,  Sp.  gr.  i.io. — Dilute  "muri- 
atic, acid  "  with  an  equal  volume  of  water.  In  addi- 
tion to  its  use  for  preparing  cuprous  chloride,  it  finds 
employment  in  neutralizing  the  caustic  solutions  which 
are  unavoidably  more  or  less  spilled  during  their  use. 

Acid  Cuprous  Chloride. — The  directions  given  in 
the  various  text-books  being  troublesome  to  execute, 
the  following  method,  which  is  simpler,  has  been 
found  to  give  equally  good  results.  Cover  the  bottom 
of  a  two-liter  bottle  with  a  layer  of  copper  oxide  or 
"  scale  -f  in.  deep,  place  in  the  bottle  a  number  of 
pieces  of  rather  stout  copper  wire  reaching  from  top 
to  bottom,  sufficient  to  make  a  bundle  an  inch  in 
diameter,  and  fill  the  bottle  with  common  hydrochloric 
acid  of  i.io  sp.  gr.  The  bottle  is  occasionally  shaken, 
and  when  the  solution  is  colorless,  or  nearly  so,  it  is 
poured  into  the  half-liter  reagent  bottles,  containing 
copper  wire,  ready  for  use.  The  space  left  in  the 
stock  bottle  should  be  immediately  filled  with  hydro- 
chloric acid  (i.io  sp.  gr.). 

34 


REAGENTS  AND   LABORATORY.  35 

By  thus  adding  acid  or  copper  wire  and  copper 
oxide  when  either  is  exhausted,  a  constant  supply  of 
this  reagent  may  be  kept  on  hand. 

The  absorption  capacity  of  the  reagent  per  cc.  is, 
according  to  Winkler,  15  cc.  CO;  according  to 
Hempel  4  cc.  The  author's  experience  with  Orsat's 
apparatus  gave  I  cc. 

Care  should  be  taken  that  the  copper  wire  does  not 
become  entirely  dissolved  and  that  it  extend  from  the 
top  to  the  bottom  of  the  bottle;  furthermore  the 
stopper  should  be  kept  thoroughly  greased  the  more 
effectually  to  keep  out  the  air,  which  turns  the  solution 
brown  and  weakens  it. 

Ammoniacal  Cuprous  Chloride.  —  The  acid  cu- 
prous chloride  is  treated  with  ammonia  until  a  faint 
odor  of  ammonia  is  perceptible;  copper  wire  should 
be  kept  in  it  similarly  to  the  acid  solution.  This 
alkaline  solution  has  the  advantage  that  it  can  be 
used  when  traces  of  hydrochloric  acid  vapors  might 
be  harmful  to  the  subsequent  determinations,  as,  for 
example,  in  the  determination  of  hydrogen  by  absorp- 
tion with  palladium.  It  has  the  further  advantage 
of  not  soiling  mercury  as  does  the  acid  reagent. 

Absorption  capacity,  i  cc.  absorbs  I  cc.  CO. 

Cuprous  chloride  is  at  best  a  poor  reagent  for  the 
absorption  of  carbonic  oxide;  to  obtain  the  greatest 
accuracy  where  the  reagent  has  been  much  used,  the 
gas  should  be  passed  into  a  fresh  pipette  for  final 
absorption,  and  the  operation  continued  until  two 
consecutive  readings  agree  exactly.  The  compound 
formed  by  the  absorption — possibly  Cu2COCl2 — is  very 
unstable,  as  carbonic  oxide  may  be  freed  from  the 


36  GAS  AND   FUEL  ANALYSIS. 

solution  by  boiling  or  placing  it  in  vacuo;  even  if  it 
be  shaken  up  with  air,  the  gas  is  given  off,  as  shown 
by  the  increase  in  volume  and  subsequent  diminution 
when  shaken  with  fresh  cuprous  chloride. 

Potassium  Hydrate. — (a)  For  carbon  dioxide  de- 
termination, 500  grams  of  the  commercial  hydrate  is 
dissolved  in  I  liter  of  water. 

Absorption  capacity,  I  cc.  absorbs  40  cc,  CO2. 

(b)  For  the  preparation  of  potassium  pyrogallate 
for  special  work,  120  grams  of  the  commercial  hydrate 
is  dissolved  in  100  cc.  of  water. 

Potassium  Pyrogallate. — Except  for  use  with  the 
Orsat  or  Hempel  apparatus,  this  solution  should  be 
prepared  only  when  wanted.  The  most  convenient 
method  is  to  weigh  out  5  grams  of  the  solid  acid  upon 
a  paper,  pour  it  into  a  funnel  inserted  in  the  reagent 
bottle,  and  pour  upon  it  100  cc.  of  potassium  hydrate 
(a)  or  (b).  The  acid  dissolves  at  once,  and  the  solution 
is  ready  for  use. 

If  the  percentage  of  oxygen  in  the  mixture  does 
not  exceed  28,  solution  (a)  may  be  used  ;*  if  this 
amount  be  exceeded,  (b)  must  be  employed.  Other- 
wise carbonic  oxide  may  be  given  off  even  to  the 
extent  of  6  per  cent. 

Attention  is  called  to  the  fact  that  the  use  of  potas- 
sium hydrate  purified  by  alcohol  has  given  rise  to 
erroneous  results. 

Absorption  capacity,  i  cc.  absorbs  2  cc.  O. 

Sodium  Hydrate. — Dissolve  the  commercial  hy- 
drate in  three  times  its  weight  of  water.  This  may  be 

*  Clowes,  Jour.  Soc.  Chem.  Industry,  15,  170. 


REAGENTS  AND    LABORATORY.  37 

employed  in  all  cases  where  solution  (a)  of  potassium 
hydrate  is  used.  The  chief  advantage  in  its  use  is  its 
cheapness,  it  costing  but  one  tenth  as  much  as  potas- 
sium hydrate,  a  point  to  be  considered  where  large 
classes  are  instructed.  Sodium  pyrogallate  is,  how- 
ever, a  trifle  slower  in  action  than  the  corresponding 
potassium  salt. 

ARRANGEMENT   OF   THE   LABORATORY. 

The  room  selected  for  a  laboratory  for  gas-analysis 
should  be  well  lighted,  preferably  from  the  north  and 
east.  To  prevent  changes  in  temperature  it  should 
be  provided  with  double  windows,  and  the  method  of 
heating  should  be  that  which  will  give  as  equable  a 
temperature  as  possible.  In  the  author's  laboratory, 
instead  of  the  usual  tables,  shelves  are  used,  18  inches 
wide  and  \\  inches  thick,  best  of  slate  or  soapstone, 
firmly  fastened  to  the  walls,  30  inches  from  the  floor; 
the  Orsat  apparatus,  when  not  in  use,  may  be  sus- 
pended from  these.  The  reagents  are  contained  in 
half-liter  bottles  fitted  with  rubber  stoppers,  placed 
upon  a  central  table  convenient  to  all.  Here  are 
found  scales,  funnels  and  graduates  for  use  in  making 
up  reagents.  Distilled  water  is  piped  around'  to  each 
place  by  -J-inch  tin  pipe  and  ^--inch  rubber  tubing 
from  a  J-inch  "main,"  being  supplied  at  the  tem- 
perature of  the  room  from  bottles  placed  about  six 
feet  above  the  laboratory  shelves.  A  supply  of  a 
gallon  per  day  per  student  should  be  provided. 

At  the  right  of  each  place  is  fixed  a  sand-glass  of 
cylindrical  rather  than  conical  form,  graduated  to 
minutes  for  the  draining  of  the  burettes._^_The  "egg- 

Tue 

OF  THK 

UNIVERSITY 


38  GAS  AND   FUEL  ANALYSIS. 

timers  "  found  in  kitchen-furnishing  stores  serve  the 
purpose  admirably. 

11  Unknown  gases  "  for  analysis  are  best  contained 
in  a  Muencke  double  aspirator,  Fig.   12,  where  they 


FIG.  12. — MUENCKK'S  ASPIRATOR. 

can  be  thoroughly  mixed  before  distribution  and  con- 
veyed by  a  pipe  to  the  central  table. 

Finally,  the  laboratory  should  contain  a  stone-ware 
sink  provided  with  an  efficient  trap  of  the  same 
material,  to  prevent  mercury  from  being  carried  into 
and  corroding  the  lead  waste-pipes. 

Drawers  should  be  provided  with  compartments  for 
various  sizes  of  rubber  connectors,  pinchcocks,  glass 
tubing,  stoppers  and  fittings,  and  tools.  When  work- 
ing with  the  Orsat  apparatus  alone,  three  feet  of  shelf 


REAGENTS   AND    LABORATORY.  39 

space  may  be  allowed  to  each  student;  when  using  this 
with  another,  as,  for  example,  the  Bunte,  another 
foot  should  be  added. 

The  course  which  the  writer  has  been  in  the  habit 
of  giving  to  the  Mechanical  and  Electrical  Engineers 
embraces  two  exercises  in  the  laboratory  of  two  hou:s 
each,  supplemented  with  four  hours  of  lectures.  The 
students  in  the  laboratory  make  an  analysis  of  air  and 
an  "  unknown"  furnace-gas,  take  and  analyze  an 
actual  sample  of  chimney-gas,  and  make  the  calculation 
of  heat  lost  and  air  used.  In  the  lectures,  the  subject 
of  gas-analysis  and  its  other  applications,  and  of  fuels, 
their  origin,  description,  preparation,  analysis,  and 
determination  of  heating  value,  are  described. 


CHAPTER    VI. 

FUELS— SOLID,   LIQUID,  AND  GASEOUS:  THEIR 
DERIVATION   AND   COMPOSITION. 

The  substances  employed  as  fuels  are: 

a.  SOLID  FUELS. — Wood,  peat,  brown,  bituminous 
and   anthracite  coal,   charcoal,    coke,   and   oftentimes 
various   waste  products,  as  sawdust,   bagasse,   straw, 
and  spent  tan. 

b.  LIQUID  FUELS. — Crude  petroleum  and  various 
tarry  residues. 

c.  GASEOUS  FUELS. — Natural  gas,  generator,  blast- 
furnace, water,  and  illuminating  gas. 

The  essential  constituents  in  all  these  are  carbon  and 
hydrogen;  the  accessory,  oxygen,  nitrogen,  and  ash; 
and  the  deleterious,  water,  sulphur,  and  phosphorus. 

a.  SOLID  FUELS. 

Wood  is  composed  of  three  substances — cellulose, 
or  woody  fibre  (C8H10O5)M  ;  the  components  of  the  sap, 
the  chief  of  which  is  lignine,  a  resinous  substance  of 
identical  formula  with  cellulose;  and  water.  The 
formation  of  cellulose  from  carbon  dioxide  and  water 
may  be  represented  by  the  equation 

6CO,  +  5H20  =  C6Hlf,06  +  602. 

The  amount  of  water  which  wood  contains  determines 
its  value  as  a  fuel.     This  varies  from  29  per  cent  in  ash 

40 


FUELS— SOLID,  LIQUID,  AND  GASEOUS.  41 

to  50  per  cent  in  poplar;  it  varies  also  with  the  season 
at  which  the  wood  is  cut,  being  least  when  the  sap  is  in 
the  roots — in  December  and  January.  This  difference 
may  amount  to  10  per  cent  in  the  same  kind  of  wood. 

The  harder  varieties  of  wood  make  the  best  fuel,  a 
cord  of  seasoned  hardwood  being  about  equal  to  a  ton 
of  coal.  Yellow  pine,  however,  has  but  half  this 
value;  the  usual  allowance  in  a  boiler-test  is  0.4  the 
value  of  an  equal  weight  of  coal. 

The  ash  of  wood  is  mainly  potassium  carbonate, 
with  traces  of  other  commonly  occurring  substances, 
as  lime,  magnesia,  iron,  silica,  and  phosphoric  acid. 

The  percentage  composition  of  wood  may  be  con- 
sidered as  approximately, 

Water.        Carbon.        Hydrogen.        Oxygen.          Ash.  Sp.  Gr. 

20  39  4.4  35-6  I  0.5.* 

When  burned  it  yields  about  4000  C.  per  kilo,  and 
requires  6  times  its  weight  of  air  or  9.22  cu.  m.  (148 
cu.  ft.  per  pound)  for  its  combustion. 

Peat,  though  finding  considerable  application  in 
Europe,  is  but  little  used  in  this  country.  It  is  pro- 
duced by  the  slow  decay  under  water  of  certain  swamp 
plants,  more  especially  the  mosses  (Sphagnaceae), 
evolving  methane  (CH4)  (marsh-gas)  and  carbon  diox- 
ide (CO,). 

It  contains  considerable  moisture,  from  20  to  50 
per  cent,  and  10  per  cent  even  when  "  thoroughly 
dry."  Thirty  per  cent  of  its  available  heat  is  em- 
ployed in  evaporating  this  moisture.  The  high  con- 
tent of  ash,  from  3  to  30  per  cent,  averaging  15  per 
cent,  also  diminishes  its  value  as  a  fuel. 
*  Mills  &  Rowan,  Fuels,  p.  n. 


42  GAS  AND   FUEL   ANALYSIS. 

The  ash  of  peat  differs  from  that  of  wood  in  contain- 
ing little  or  no  potassium  carbonate. 

The  percentage  composition  of  peat  may  be  consid- 
ered as  approximately, 

Water.        Carbon.     Hydrogen.      Oxygen.    Nitrogen.       Ash.        Sp.  Gr. 
16.4  41.0  4.32  3.8  2.6  11.9         1.05. 

Such  peat  is  about  equivalent  to  wood  in  its  heating 
effect,  one  pound  evaporating  from  4.5  to  5  pounds 
of  water. 

Coal. — Geologists  tell  us  that  coal  was  probably 
produced  by  the  decay  under  fresh  water  of  plants 
belonging  principally  to  the  Conifer,  Fern  and  Palm 
families;  these  flourished  during  the  Carboniferous 
Age  to  an  extent  which  they  never  approached  before 
or  since.  Representatives  of  the  last  family,  which 
it  is  thought  produced  most  of  the  coal,  have  been 
found  2  to  4  feet  in  diameter  and  80  feet  in  height. 

By  their  decay,  carbon  dioxide  "  choke-damp," 
marsh-gas  "  fire-damp,"  and  water  were  evolved. 
The  change  might  be  represented  by  the  equation 

6C.H,.  0.  =  7CO,  +  3CH,  +  I4H80  +  C..H..O.. 

Cellulose.  Bituminous  Coal. 

Some  idea  of  the  density  of  the  vegetation  and  the 
time  required  may  be  obtained  from  the  fact  that  it 
has  been  calculated  that  100  tons  of  vegetable  matter 
— the  amount  produced  per  acre  per  century — if  com- 
pressed to  the  specific  gravity  of  coal  and  spread  over 
an  acre  would  give  a  layer  less  than  0.6  of  an  inch 
thick.  Now  four  fifths  of  this  is  lost  in  the  evolution 
of  the  gaseous  products,  giving  as  a  result  an  accumu- 


FUELS— SOLID,  LIQUID,  AND  GASEOUS,  43 

lation  of  one  eighth  of  an  inch  per  century,  or  one  foot 
in  10,000  years.* 

Brown  Coal  or  Lignite  may  be  regarded  as  forming 
the  link  between  wood  and  coal ;  geologically  speaking 
it  is  of  later  date  than  the  true  coal.  Most  of  the  coal 
west  of  the  Rocky  Mountains  is  of  this  variety. 

As  its  name  denotes,  it  generally  is  of  brown  color 
— although  the  western  coal  is  black — and  has  a  con- 
choidal  fracture.  It  contains  a  large  quantity  of 
water  when  first  mined,  as  much  as  60  per  cent,  and 
when  "  air-dry  "  from  15  to  20  per  cent.  The  per 
cent  of  ash  is  also  high,  from  i  to  20  per  cent. 

The  percentage  composition  of  brown  coal  may  be 
considered  as  approximately, 

Water.       Carbon.     Hydrogen.     Oxygen  and  Nitrogen.    Ash.  Sp.  Gr. 

18.0          50.9          4.6  16.3  10.2  1.3. 

Bituminous  Coal. — This  is  the  variety  from  which  all 
the  following  coals  are  supposed  to  have  been  formed, 
by  a  process  of  natural  distillation  combined  with  pres- 
sure. According  to  the  completeness  of  this  process 
we  have  specimens  which  contain  widely  differing  quan- 
tities of  volatile  matter.  This  forms  the  true  basis  for 
the  distinguishing  of  the  varieties  of  coal.  In  ordinary 
bituminous  coal  this  volatile  matter  amounts  to  30  or 
40  per  cent.  Three  varieties  of  bituminous  coal  are 
ordinarily  distinguished,  as  follows: 

Dry  or  non-caking — those  which  burn  freely  with  but 
little  smoke  and — as  the  name  denotes — do  not  cake 

*  In  case  the  student  desires  to  follow  in  a  more  extended 
manner  the  geology  of  coal,  reference  may  be  had  to  Le  Conte's 
"  Elements  of  Geology,"  pp.  345-414  3d  ed, 


44  GAS  AND   FUEL  ANALYSIS. 

together  when  burned.  The  coals  from  Wyoming 
are  an  example  of  this  class. 

Caking — those  which  produce  some  smoke  and  cake 
or  sinter  together  in  the  furnace.  An  example  of 
these  is  the  New  River  coal. 

Fat  or  Long-flaming — those  producing  much  flame 
and  smoke  and  do  or  do  not  cake  in  burning;  volatile 
matter  50  per  cent  or  more.  Some  of  the  Nova 
Scotia  coals  belong  to  this  class. 

Bituminous  coal  varies  much  in  its  composition — is 
black  or  brownish  black,  soft,  friable,  lustrous,  and  of 
specific  gravity  of  1.25  to  1.5. 

Moisture  varies  from  0.25  to  8  per  cent,  averaging 
about  5. 

The  percentage  composition  of  bituminous  coal  may 
be  considered  as  approximately,* 

Water.      Carbon.     Hydrogen.    Oxygen.     Nitrogen.         Ash.        Sulphur. 
0.6  80.5  4.9  5.4  2.1  5.8  0.7. 

Semi-Bituminous  or  Semi-Anthracite  Coal  is  upon 
the  border-line  between  the  preceding  and  the  follow- 
ing variety;  it  is  harder  than  bituminous,  contains 
less  volatile  matter  (15  to  20  per  cent),  and  burns 
with  a  shorter  flame.  An  example  of  this  is  the 
Pocahontas  coal. 

The  percentage  composition  of  semi-bituminous  and 
semi-anthracite  coal  may  be  considered  to  be  appioxi- 
mately,* 

Water.        Carbon.     Hydrogen.    Oxygen.     Nitrogen.        Ash.        Sulphur. 
1.8  77-4  4-7  3-7  2.0  9.5  0.9. 

Anthracite  Coal  is  the  hardest,   most  lustrous,  and 
densest  of  all  the  varieties  of  coal,  having  a  specific 
*  H.  J.  Williams. 


FUELS— SOLID,  LIQUID,  AND   GASEOUS.  45 

gravity  of  1.3  to  1-75;  it  contains  the  most  carbon 
and  least  hydrogen  and  volatile  matter  (5  to  10  per 
cent).  It  has  a  vitreous  fracture  and  kindles  with 
difficulty,  burning  with  a  feeble  flame,  giving  little  or 
no  smoke  and  an  intense  fire.  The  Lehigh  coal  is  an 
excellent  example  of  this  class. 

The  percentage  composition  of  antliracite  coal  may 
be  considered  as  approximately,* 

Water.        Carbon.     Hydrogen.     Oxygen.     Nitrogen.        Ash.        Sulphur. 
3.2  82.4  2.5  2.7  0.8  7.8  0.6. 

The  ash  of  coal  varies  from  I  to  20  per  cent  and  is 
mainly  clay — silicate  of  aluminium — with  traces  of 
lime,  magnesia,  and  iron.  When  coal  is  burned  it 
yields  from  7500  to  8000  C.  and  requires  about  12  times 
its  weight  of  air,  18.44  cu-  m-  Per  kilo  or  296  feet  per 
pound.  For  the  greatest  economy  Scheurer-Kestner  f 
found  that  this  should  be  increased  from  50  to  100 
per  cent. 

Charcoal  is  prepared  by  the  distillation  or  smoulder- 
ing of  wood,  either  in  retorts,  where  the  valuable 
by-products  are  saved,  or  in  heaps.  It  should  be 
jet-black,  of  bright  lustre  and  conchoidal  fracture. 

When  wood  is  charred  in  heaps  only  about  20  per 
cent  of  its  weight  in  charcoal  is  obtained — 48  bushels 
per  cord,  or  about  half  the  percentage  of  carbon. 
When  retorts  or  kilns  are  employed,  the  yield  is  in- 
creased to  30  per  cent,  and  40  per  cent  of  pyroligneous 
acid  of  10  per  cent  strength,  with  4  per  cent  of  tar, 
are  obtained. 

*H.  J.  Williams. 

f  Jour.  Soc.  Chem.  Industry,  7,  616, 


46  GAS  AND    FUEL   ANALYSIS. 

The  percentage  composition  of  wood-charcoal  may  be 
considered  as  approximately, 

Carbon.  Ash.  Sp.  Gr. 

97.0  3.0  0.2 

Coke  is  prepared  by  the  distillation  of.  bituminous 
coal  in  ovens;  these  are  of  two  types,  those  in  which 
the  distillation-products  are  allowed  to  escape — the 
"  beehive  "  ovens — and  those  in  which  they  are  care- 
fully saved,  as  the  Otto-Hoffman,  Semet-Solvay, 
Simon-Carves',  and  others. 

From  63  to  65  per  cent  of  the  weight  of  the  coal  is 
obtained  as  coke  in  the  "  beehive  "  ovens,  while  in 
the  Semet-Solvay  80  per  cent  is  obtained,  together 
with  by-products,  increasing  the  total  value  of 
the  output  nearly  sevenfold.  Good  coke  should 
possess  a  silvery  lustre,  a  cellular  structure,  a  metallic 
ring,  contain  practically  no  impurities,  and  be  capable 
of  bearing  a  heavy  burden  in  the  furnace. 

The  analysis  of  Connellsville  coke  with  the  coal 
from  which  it  is  prepared  is  given  below. 

Water.      Volatile  Matter.       Carbon.          Sulphur.  Ash. 

Coal          1.26  30.1  59.62  0.78  8.23 

Coke         0.03  1.29  89.15  0.084  9-52 

The  Minor  Solid  Fuels. 

Sawdust  and  Spent  Tan-bark  find  occasional  use, 
their  value  depending  upon  the  quantity  of  moisture 
they  contain.  With  57  per  cent  of  moisture  I  pound 
of  tan-bark  gave  an  evaporation  of  4  pounds  of  water. 

Wheat  Straw  finds  application  as  fuel  in  agricul- 
tural districts,  3J  pounds  being  equal  to  I  pound  of 
coal.  Upon  sugar-plantations  the  crushed  cane  or 
Bagasse,  partially  dried,  is  extensively  used  as  a 


FUELS— SOLID,  LIQUID,  A 


fuel.  With  16  per  cent  of  moisture  an  evaporation 
of  2  pounds  of  water  per  pound  of  fuel  has  been 
obtained. 

b.  LIQUID  FUELS. 

These  consist  of  petroleum  and  its  products,  and 
various  tarry  residues  from  processes  of  distillation, 
as  from  petroleum,  coking-ovens,  wood  and  shale. 
Liquid  fuel  possesses  the  advantage  that  it  is  easily 
manipulated,  and  the  fire  is  of  very  equable  tempera- 
ture, very  hot,  and  practically  free  from  smoke. 

Regarding  the  origin  of  petroleum,  many  theories 
have  been  proposed.  That  of  Engler,*  that  it  was 
formed  by  the  distillation  under  pressure  of  animal  fats 
and  oils,  the  nitrogenous  portions  of  the  animals  pre- 
viously escaping  as  amines,  seems  most  probable;  it 
has  yielded  the  best  results  of  any  hypothesis  when 
tested  upon  an  industrial  scale. 

Crude  Petroleum  varies  greatly  in  color  according 
to  the  locality;  it  is  usually  yellowish,  greenish,  or 
reddish  brown,  of  benzine-like  odor,  and  sp.  gr.  of  0.78 
to  0.80.  It  "  flashes"  at  the  ordinary  temperature; 
hence  great  care  should  be  employed  in  its  use  and 
storage.  \\&  percentage  composition  is  shown  below. 

Carbon.  Hydrogen. 

84.0-85.0  16.0-15.0 

It  is  more  than  twice  as  efficient  as  the  best  anthra- 
cite coal.  In  practice  16  pounds  of  water  per  pound 
of  petroleum  have  been  evaporated,  and  an  efficiency 
of  20,200  C.  was  obtained  as  against  8603  C.  for 
anthracite. 

*  Jour.  Soc.  Chem.  Industry,  14,  648. 


4  8  GAS  AND   FUEL  ANALYSIS. 

c.  GASEOUS  FUELS. 

Natural  Gas  is  usually  obtained  when  boring  for 
petroleum  and  consists  mainly  of  methane  and  hydro- 
gen, although  the  percentage  varies  with  the  locality. 
The  Findlay,  Ohio,*  gas  is  of  the  following  composi- 
tion: 

CH4  H  N  O          C2H4        C02         CO          H2S        Sp.  Gr. 

92.6          2.3          3.5  0.3          0.3          0.3          0.5          0.2          0.57 

Blast-furnace,  Producer,  or  Generator  Gas  is  the 

waste  gas  issuing  from  the  top  of  a  blast-furnace  or 
obtained  by  partially  burning  coal  by  a  current  of  air 
in  a  special  furnace — a  gas-producer  or  generator.  It 
is  mainly  carbonic  oxide  and  nitrogen. 

CO  N  CO,  II          CH4  Sp.  Gr. 

Blast-furnace  gas    34.3         63.7         0.6         1.4 
Producer  gas  23.5         65.  1.5         6.0         3.0  i.o 

Fischer  f  states  that  i  kg.  coal  gives  4.5  cu.  m.  gas 
of  4760  C.,  the  coal  giving  7950  C.  or  about  60  per 
cent  of  the  value  of  the  coal.  This  is  calculated  on 
the  heating  effect  of  the  cold  gas;  if  it  were  used  hot 
as  it  leaves  the  producer,  at  about  690°  C.,  the  heating 
effect  would  be  increased  by  850  C. 

Water-gas. — If,  instead  of  passing  simply  air  over 
hot  coal,  water-vapor  be  employed,  it  is  decomposed, 
giving  carbonic  oxide  and  hydrogen,  according  to  the 
equation  H.2O  -f-  C  =  CO  +  H2 ,  and  the  resulting 
mixture  is  called  water-gas.  Its  percentage  composition 
is  as  follows : 

CO  H  CH4         CO2  N  O  Sp  Gr. 

45.8  45.7  2.0  4.0  2.0  0.5  0.57 

*  Orton,  Geology  of  Ohio,  vol.  vi.  p.  137. 
|  Wagner's  Chemical  Technology. 


FUELS— SOLID,  LIQUID,  AND  GASEOUS.          49 

Fischer*  states  that  I  kg.  coal  gives  about  1.2  cu. 
m.  gas,  or  about  58  per  cent  of  the  heating  value. 

Coal  or  Illuminating  Gas  was  formerly  produced 
by  the  distillation  of  bituminous  coal;  it  is  at  present 
largely  made  by  the  enriching  of  water-gas.  "  Gas- 
oil,"  a  crude  naphtha,  is  blown  into  the  water-gas 
generator  and  changed  to  a  permanent  gas  by  the 
heat.  Coal-gas  is  of  the  following  composition: 

H  CH4  CO          C2H4  C02  N  O        Sp.  Gr. 

47.0         40.5          6.0         4.0         0.5         1.5        0.5         0.4 

I  kilo  of  coal  gives  about  0.3  cubic  meter  of  gas,  or 
about  20  per  cent  of  the  heating  value. 

Heating  Value  of  these  Gases. 

Prof.  Orton  \  gives  the  following  relative  values  of 
the  various  gases.  Omitting  in  all  cases  losses  by 
radiation  and  assuming  that  the  gases  escape  at  500° 
F.  and  are  burned  with  20  per  cent  excess  of  air, 
1000  cu.  ft.  of  each  gas  would  evaporate  from  60°  F. 
to  212°  F.  the  following  quantities  of  water  expressed 
in  pounds: 

Natural    gas 893 

Coal  "    591 

Water        "    262 

Producer  "    115 

Natural  gas  requires  for  its  combustion  about 
eleven  times  its  volume  of  air,  allowing  for  20  per 
cent  excess. 


*  Taschenbuch  fur  Feuerungs  Techniker,  p.  27. 
f  Ohio  Geology,  vol.  vi.  p.  544. 


CHAPTER   VII. 

METHODS    OF    ANALYSIS    AND     DETERMINATION 
OF  THE    HEATING  VALUE   OF   FUEL. 

SAMPLING. 

A  FEW  representative  lumps  or  shovelfuls  are  taken 
from  each  barrow  or  from  various  points  in  the  pile, 
and  the  whole  spread  out  in  a  low  circular  heap. 
Diameters  are  drawn  at  right  angles  in  it  and  opposite 
quarters  taken,  these  mixed  and  treated  similarly  to  the 
whole  sample.  The  operation  is  continued  until  a 
sample  of  a  few  pounds  is  obtained.  This  is  roughly 
crushed  and  samples  taken  at  different  points  for  the 
moisture  determination;  it  is  then  further  quartered 
down  until  a  sample  of  200  grams  which  passes  a  60- 
mesh  sieve  is  obtained. 

The  methods  employed  in  the  analysis  of  fuels  are 
largely  a  matter  of  convention,  various  methods  giving 
varied  results;  for  example,  it  is  well-nigh  impossible 
to  obtain  accurately  the  percentage  of  moisture  in 
coal,  a,s  when  heated  sufficiently  hot  to  expel  the 
water  some  of  the  hydrocarbons  are  volatilized. 

Moisture. — Dry  from  I  to  2  grams  of  the  sample  in 
a  watch-glass  exactly  one  hour  at  105°  to  110°  C.* 

Coke  and  Volatile  Matter. — Carry  about  one  gram 
of  the  sample,  weighed  into  a  platinum  crucible,  to 

*  See  an  article  by  Hale,  Proc.  Am.  Soc.  Mech.  Eng.  1896. 

50 


FUEL  ANALYSIS— HEATING    VALUE.  51 

the  blast-lamp  table;  heat  for  exactly  three  and  one 
half  minutes  by  the  watch  in  the  hottest  part  of  the 
Bunsen  flame,  it  being  from  7  to  8  inches  long,  and 
then  for  exactly  three  and  one  half  minutes  by  the 
blast-lamp.  The  residue  is  coke.  With  anthracite 
coals  the  heating  over  the  Bunsen  burner  is  omitted. 

Carbon  and  Hydrogen. — These  are  determined  by 
burning  the  coal  in  a  stream  of  air  and  finally  in 
oxygen,  the  products  of  combustion,  carbon  dioxide 
and  water,  being  absorbed  in  potassium  hydrate  and 
calcium  chloride. 

Apparatus  Required. — Combustion-furnace  similar 
to  that  shown  in  Fig.  13.  Combustion-tube  filled. 


FIG.  13.— COMBUSTION-FURNACE. 

Potash-bulbs  with  straight  chloride  of  calcium  tube 
filled.  Chloride  of  calcium  tube  filled.  Oxygen- 
holder,  drying  and  purifying  apparatus.  Porcelain 
boat,  desiccator,  tongs,  -J-inch  rubber  tubing.  Ana- 
lytical balance. 

The  combustion-tube  is  of  hard  glass,  \  inch  in  in- 


52  GAS  AND   FUEL   ANALYSIS. 

ternal  diameter  and  36  inches  long,  closed  with  per- 
forated rubber  stoppers.  One  end — called  the  front 
end — is  filled  with  a  layer  of  copper  oxide  12  inches 
long,  held  in  place  by  plugs  of  asbestos  coming 
within  4  inches  of  the  stopper.  In  coals  rich  in  sul- 
phur the  oxide  is  partially  replaced  by  a  layer  of 
chromate  of  lead  2  inches  long.  The  position  of  the 
boat  containing  the  coal  is  immediately  behind  this 
copper  oxide;  behind  the  boat  is  placed  an  oxidized 
copper  gauze  roll,  6  inches  long.  Before  making  the 
combustion,  the  tube  and  contents  should  be  heated 
to  a  dull  red  heat  in  a  stream  of  oxygen  freed  from 
moisture  and  carbon  dioxide  by  the  purifying  appa- 
ratus, to  burn  any  dust  and  dry  the  contents;  it  is 
then  ready  for  use. 

The  potash-bulbs  are  an  aggregation  of  five  bulbs, 
the  three  lowest  filled  with  potassium  hydrate  of  1.27 
sp.  gr.,  the  other  two  serving  as  safety-bulbs,  pre- 
venting the  liquid  from  being  carried  over  into  the 
connectors.  They  should  be  connected  further  with  a 
chloride  of  calcium  tube  to  absorb  any  moisture  carried 
away  by  the  dry  gas.  When  not  in  use  they  should 
be  closed  with  connectors  carrying  glass  plugs.  Before 
weighing  they  should  stand  at  least  fifteen  minutes  in 
the  balance-room  to  attain  its  temperature ;  the  weight 
should  be  to  milligrams  and  without  the  connectors. 

The  chloride  of  calcium  tube  is  of  U  form,  provided 
with  bulbs  for  the  condensation  of  the  water;  the 
granular  calcium  chloride  is  kept  in  place  by  cotton 
plugs,  and  the  stopper  neatly  sealed  in  with  sealing- 
wax.  As  calcium  chloride  may  contain  oxide  which 
would  absorb  the  carbon  dioxide  formed,  a  current  o* 


FUEL   ANALYSIS— HEATING    VALUE.  53 

dry  carbon  dioxide  should  be  passed  through  the  tube 
and  thoroughly  swept  out  by  dry  air  before  use. 

The  chloride  of  calcium  tube  like  the  potash-bulbs 
should  be  placed  in  the  balance-room  fifteen  minutes 
before  weighing  and,  if  the  balance-case  be  dry,  may 
be  weighed  without  the  connectors.  It  should  be 
weighed  to  milligrams. 

The  oxygen-holder  may  be  like  the  Muencke  aspi- 
rator, Fig.  12.  The  oxygen  should  be  purified  by 
passing  through  potassium  hydrate  and  over  calcium 
chloride. 

Operation. — The  front  stopper  of  the  combustion- 
tube  is  slipped  carefully  upon  the  stem  of  the  chloride 
of  calcium  tube  and  this  connected  to  the  potash- 
bulbs;  02  to  0.3  gram  of  the  coal  is  carefully 
weighed  into  the  porcelain  boat  (to  o.  i  mg.),  the  roll 
removed,  and  the  boat  inserted  behind  the  layer  of 
copper  oxide,  and  the  roll  and  stopper  replaced. 
The  tube  is  now  ready  to  be  heated. 

The  front  of  the  copper  oxide  is  first  heated,  the 
heat  being  gradually  extended  back;  at  this  time  the 
rear  end  of  the  copper  roll  is  heated  and  a  slow  cur- 
rent of  purified  air  passed  through.  This  method 
of  gradual  heating  £>f  the  tube  is  followed  until  the 
layer  of  copper  oxide  and  the  rear  portion  of  the  roll 
are  at  a  dull  red  heat.  Heat  is  now  cautiously  applied 
to  the  coal  and  the  current  of  air  slackened.  The 
volatile  matter  in  the  coal  distils  off,  is  carried  into 
the  layer  of  copper  oxide  and  burned;  the  carbon 
dioxide  formed  can  be  seen  to  be  absorbed  by  the 
potassium  hydrate.  When  this  absorption  almost 
ceases,  oxygen  is  turned  on  and  the  coal  heated  until 


54  GAS  AND   FUEL  ANALYSIS. 

it  glows.  The  stream  of  oxygen  should  be  so  regulated 
as  to  produce  but  two  bubbles  of  carbon  dioxide  in 
the  bulbs  per  second.  If  the  evolution  be  faster,  the 
gas  is  not  absorbed.  When  the  coal  has  ceased  glow- 
ing, oxygen  is  allowed  to  pass  through  the  apparatus 
until  a  spark  held  at  the  exit  of  the  last  chloride  of 
calcium  tube  (on  the  bulbs)  re-inflames;  the  oxygen  is 
allowed  to  run  for  fifteen  minutes  longer.  The  current 
of  oxygen  is  now  replaced  by  purified  air,  and  the 
heat  moderated  by  turning  down  the  burners  and 
opening  the  fire-clay  tiles;  the  air  is  allowed  to  run 
through  for  twenty  minutes  to  thoroughly  sweep  out 
all  traces  of  carbon  dioxide  and  moisture.  The  bulbs 
and  U  tube  are  disconnected,  stopped  up,  allowed  to 
stand  in  the  balance-room,  and  weighed  as  before. 
The  increase  in  weight  in  the  bulbs  represents  the 
carbon  dioxide  formed ;  this  multiplied  by  the  factor 
0.2727  gives  the  carbon.  Similarly  the  increase  in  the 
U  tube,  minus  the  water  due  to  the  moisture  in  the 
coal,  represents  the  water  formed,  one  ninth  of  which 
is  hydrogen. 

Notes, — At  no  time  in  the  combustion  should  any 
water  appear  near  the  copper  roll,  as  it  is  an  indication 
that  the  products  of  combustion  have  gone  backward 
into  the  purifying  apparatus  and  hence  are  lost.  Such 
analyses  should  be  repeated.  Should  moisture  appear 
in  the  front  end,  it  may  be  gently  heated  to  expel  it. 
Both  ends  of  the  tube  should  be  frequently  touched 
with  the  hand  during  the  combustion,  and  should  be 
no  hotter  than  may  be  comfortably  borne,  as  the 
stoppers  give  off  absorbable  gases  when  highly  heated. 
Care  should  be  taken  not  to  heat  the  tube  too  hot, 


FUEL   ANALYSIS— HEATING    VALUE.  55 

fusing  the  copper  oxide  into  and  spoiling  it.  One 
tube  should  serve  for  a  dozen  determinations.  It 
should  not  be  placed  upon  the  iron  trough  of  the 
furnace,  but  upon  asbestos-paper  in  the  trough,  to 
prevent  fusion  to  the  latter. 

As  will  be  seen,  the  execution  of  a  combustion  is 
not  easy,  and  should  only  be  intrusted  to  an  experi- 
enced chemist.  The  results  obtained  are  usually  o.i 
per  cent  too  low  for  carbon  and  a  similar  amount  too 
high  for  hydrogen. 

Ash. — This  is  determined  by  weighing  the  residue 
left  in  the  boat  after  combustion,  or  by  completely 
burning  one  gram  of  the  coal  contained  in  a  platinum 
dish;  often  a  stream  of  oxygen  is  used. 

Nitrogen  is  determined  by  Kjeldahl's  method, 
which  consists  in  digesting  the  coal  with  strong  sul- 
phuric acid,  aided  by  potassium  permanganate,  until 
nearly  colorless.  The  nitrogenous  bodies  are  changed 
to  ammonia,  which  forms  ammonium  sulphate  and 
may  be  determined  by  rendering  alkaline  and  distil- 
ling the  solution. 

Sulphur  is  determined  by  Eschka's  method,  con- 
sisting in  heating  for  an  hour  one  gram  of  the  coal 
mixed  with  one  gram  of  magnesium  oxide  and  0.5 
grm.  sodium  carbonate  in  a  platinum  dish  without  stir- 
ring, using  an  alcohol-lamp,  as  gas  contains  sulphur. 
It  is  allowed  to  cool  and  rubbed  up  with  one  gram  of 
ammonium  nitrate  and  heated  for  5  to  10  minutes 
longer.  The  resulting  mass  is  dissolved  in  200  cc.  of 
water  evaporated  to  150  cc.,  acidified  with  hydro- 
chloric acid,  filtered,  and  sulphuric  acid  determined  in 
the  filtrate  in  the  usual  way  wit»h  barium  chloride. 


$6  GAS  AND   FUEL   ANALYSIS. 

Oxygen  is  determined  by  difference,  there  being 
no  direct  method  known. 

The  analysis  of  gaseous  fuels  is  conducted  upon  the 
same  principles  as  indicated  in  Chapter  II,  Hem  pel's 
apparatus  being  employed,  for  the  use  of  which  refer- 
ence may  be  had  to  the  author's  "  Handbook  of  Gas 
Analysis. ' ' 

DETERMINATION   OF   CALORIFIC    POWER   OF   SOLID 
AND    LIQUID   FUEL. 

a.  Direct  Methods. 

Many  forms  of  apparatus  have  been  proposed  for 
this  purpose;  few,  however,  with  the  exception  of 
those  employing  Berthelot's  principle — of  burning 
the  substance  under  a  high  pressure  of  oxygen — have 
yielded  satisfactory  results.  The  apparatus  of  William 
Thomson,*  and  also  that  of  Barrus,  in  which  the  coal 
is  burnt  in  a  bell-jar  of  oxygen,  yield  results  varying 
as  much  as  8  per  cent  from  the  calculated  value,  f 
It  is  further  inapplicable  to  semi-bituminous  and  an- 
thracite coals,  as  the  ash  formed  over  the  surface  pre- 
vents the  combustion  of  the  coal  beneath  it. 

Fischer's  calorimeter  +  is  similar  in  principle,  but  is 
claimed  to  give  very  good  results.  § 

Lewis  Thompson's  calorimeter,  in  which  the  coal  is 
burnt  in  a  bell-jar  by  the  aid  of  oxygen  furnished  by 
the  decomposition  of  potassium  chlorate  or  nitrate,  is 

*  Thomson,  Jour.  Soc.  Chemical  Industry,  5,  581. 
f  Ibid.,  8,  525. 

%  Zeit.  f.  angewandte  Chemie,  12,  351. 

§  Bunte,  Jour.  f.  Gasbeleucbtung  und  Wasserversorgung,  34, 
21,41, 


FUEL   ANALYSIS— HEATING    VALUE.  $7 

open  to  several  objections,  the  chief  of  which  are:  I. 
The  evolution  of  heat  due  to  the  decomposition  of  the 
oxidizing  substance  used.  2.  Loss  of  heat  due  to 
moisture  carried  off  by  the  gases  in  bubbling  through 
the  water.  The  results  which  it  gives  must  be  in- 
creased by  15  per  cent.* 

Hempel's  apparatus  f  makes  use  of  the  Berthelot 
principle:  the  coal  must  be  compressed  into  a  cylinder 
for  combustion — a  process  to  which  every  coal  is  not 
adapted  —  only  applicable  to  certain  varieties  of 
bituminous  and  brown  coal.  The  mixture  with  the 
coal  of  any  cementing  or  inflammable  substance  to 
form  these  cylinders  carries  with  it  the  necessity  of 
accurately  determining  its  calorific  power  beforehand. 

The  best  apparatus  for  the  purpose  is  probably  that 
of  Mahler,:):  modified  by  Holman  and  Williams,  the 
modifications  consisting  in  replacing  the  enamel  lining 
by  electroplating  the  inside  with  gold  and  in  improved 
methods  of  making  the  apparatus  tight. 

The  Mahler  apparatus,  Fig.  15,  consists  of  a  mild- 
steel  cylinder  Z?,  with  walls  half  an  inch  thick,  narrowed 
at  the  top  for  connection  by  a  screw-joint  with  the 
cover  carrying  the  vessel  C  to  contain  the  coal.  This 
cylinder  or  bomb  is  placed  inside  the  calorimeter  D, 
and  this  inside  a  jacket  A.  At  the  right  is  shown  a 
portion  of  the  oxygen-cylinder  and  the  gauge. 

For  the  following  directions  for  its  use  the  author 
is  indebted  to  the  kindness  of  Professor  Silas  W. 
Holman  of  the  Institute  of  Technology. 

*  Scheurer-Kestner  Jour.  Soc.  Chemical  Industry,  7,  869. 
f  Hempel,  "  Gasanalytische  Methoden,"  p.  347. 
\  Mahler,  Jour.  Soc.  Chemical  Industry,  II,  840. 


GAS  AND    FUEL   ANALYSIS. 


Preparation  of  Bomb. — Remove  the  ring  upon 
which  it  sits  in  the  calorimeter. 

Wash  out  the  bomb.  It  need  not  be  dry.  Leave 
cover  off. 

See  that  the  1  ead- ring  washer  P,  Fig.  14,  is  in  good 
condition.  Unless  its  upper  surface 
is  fairly  smooth  the  cover  cannot  be 
tightly  closed.  Repeated  screwing 
on  of  the  cover  raises  a  burr  of  lead. 
When  this  becomes  noticeable  it  must 
be  removed  by  cutting  with  a  knife- 
blade.  If  there  is  difficulty  in  mak- 
ing the  cover  tight,  it  is  most  likely 
to  be  due  to  this  cause. 

Grease  the  screw  5  upon  the  out- 
side of  the  bomb  slightly  with  tallow 
or  a  heavy  oil,  but  be  sure  that  none 
of  the  grease  gets  beyond  the  lead 
washer. 
FIG.  14.— MAHLER'S  Secure  the  bomb  very  firmly  in  the 

BOMB.  heavy  clamp  on  the  table. 

Place  the  top  on  a  ring  or  in  a  clamp  of  a  lamp-stand 
and  in  an  upright  position. 

Put  in  position  the  platinum  tray  C  and  the  rod  E, 
Fig.  15. 

Twist  on  the  loop  of  ignition-wire  (fine  platinum 
or  iron).  This  must  make  good  electrical  contact 
with  both  E  and  the  pan  or  its  supporting  rod. 
Failing  this  the  current  will  not  flow  to  fuse  the  wire. 
Failure  to  ignite  is  almost  always  traceable  to  this 
cause. 

Pour  into  the  tray  a  known  weight  of  the  substance 


FUEL  ANALYSIS— PIEA  TING    VALUE.  59 

to  be  burned.  If  this  be  coal,  slightly  over  one  gram 
should  be  used.  It  is  usually  best  inserted  from  a 
small  test-tube  weighed  before  and  after,  with  due 
precautions  against  loss. 

The  ignition-wire  should  dip  well  into  the  coal. 

The  fineness  required  in  the  combustible  depends 


FIG.  15. — MAHLER'S  APPARATUS  COMPLETE. 

upon  its  nature.  Anthracite  coal  should  be  .in  a  very 
fine  powder.  Trial  will  show  whether  any  unburned 
grains  remain,  indicating  that  the  combustible  is  too 
coarse. 

The  standard  which  carries  the  pressure-gauge 
should  be  screwed  to  the  table  near  the  bomb-clamp, 
and  the  oxygen  cylinder  must  be  placed  near  by  so 
that  the  three  may  be  easily 
copper  tube. 


60  GAS  AND   FUEL   ANALYSIS. 

The  top  carrying  the  charge  is  then  cautiously  (to 
avoid  loss  of  charge  by  jarring  or  draft)  transferred  to 
the  bomb  and  screwed  carefully  home.  The  lifting  is 
best  done  by  hooking  the  fingers  beneath  the  milled 
head  at  the  top  of  the  valve-screw  R.  The  top  must 
be  set  up  hard  by  the  wrench  which  takes  the  large 
nut  cut  on  the  cover.  In  setting  this  up  it  is  desirable 
to  use  no  more  force  than  is  necessary  to  secure  a  gas- 
tight  bearing  of  the  tongue  of  the  cover  against  the 
lead  washer  P.  Just  the  force  required  can  only  be 
learned  by  experience,  but  it  is  always  considerable. 
A  slight  leak  is  unimportant,  but  it  is  not  difficult  to 
secure  a  tight  seal  if  the  lead  washer  be  kept  in  good 
condition. 

To  fill  with  oxygen  proceed  as  follows: 

Screw  down  the  valve-screw  R  gently  to  close  the 
valve.  Connect  the  copper  tube  to  the  oxygen-tank 
gauge,  and  to  the  bomb  at  N.  See  that  there  are 
leather  washers  at  the  joints.  Turn  the  connecting 
nuts  firmly  but  not  violently  home.  The  connections 
to  the  oxygen-tank  and  gauge  are  usually  left  undis- 
turbed, and  only  that  at  N  has  to  be  made  each  time. 

It  is  now  necessary  to  test  for  leakage  in  the  con- 
nections. To  do  this,  as  R  is  closed,  it  is  only  neces- 
sary to  open  the  oxygen-tank  cautiously  by  means  of 
its  wrench  until  the  gauge  indicates  5  or  10  atmos- 
pheres and  then  close  it.  As  the  tank  when  freshly 
charged  has  a  pressure  of  120  atmospheres,  and  the 
gauge  reads  only  to  35  atmospheres,  care  must  be  used 
in  all  manipulations  not  to  overstrain  the  gauge,  also 
avoid  suddenly  releasing  the  pressure  on  the  gauge. 
When  this  pressure  is  on,  any  leak  in  the  connections 


FUEL   ANALYSIS— HEATING    VALUE.  6 1 

will  be  indicated  by  a  drop  in  the  gauge  reading.  If 
a  leak  exists,  it  must  be  removed  or  rendered  extremely 
slow  before  proceeding  further.  It  is  most  likely  to 
be  found  in  the  joints,  which  must  be  tightened  one 
by  one  until  the  leak  stops. 

Now  to  fill  the  bomb  it  is  next  necessary  to  open 
R.  This  could  be  done  by  merely  turning  back  the 
milled  head,  or  the  nut  just  above  it.  But  as  this 
would  put  a  twist  into  the  copper  connecting-tube 
(which  many  times  repeated  would  break  it),  the  better 
way  is,  holding  one  wrench  in  each  hand,  to  loosen 
the  connecting  nut  above  N  by  a  half-turn,  holding  R 
by  the  wrench  and  nut,  then  to  turn  the  nut  open 
a  half-turn  or  until  it  is  again  tight  in.  This  leaves 
the  connections  tight  and  R  open  into  the  bomb.  The 
oxygen  is  then  turned  slowly  on,  and  the  bomb 
gradually  fills.  If  a  gram  of  coal  is  to  be  burned,  a 
pressure  of  25  atmospheres  gives  the  proper  amount  of 
gas  in  the  bomb.  Note  that  the  valve  R  and  the  inlet- 
tube  have  small  borings.  Thus  the  inflow  of  gas  will 
be  slow  and  the  pressure  in  the  connecting-tube  will 
be  higher  than  in  the  bomb.  If,  therefore,  the  tank 
be  closed  quickly,  the  gauge-reading  will  fall  somewhat 
until  these  pressures  equalize,  and  will  then  remain 
stationary  unless  there  is  a  leak.  The  tank-cock  must 
always  be  kept  well  under  control  to  avoid  overcharg- 
ing either  gauge  or  bomb. 

When  the  bomb  is  full,  close  first  the  tank-cock. 
Then,  to  close  R,  put  the  wrenches  on  the  nuts  and, 
holding  one  from  turning,  set  the  other  down  until  R 
is  tight,  but  not  too  tight.  Avoid  straining  R,  which 
closes  tight  very  easily.  By  this  method  the  copper 


62  GAS  AND    FUEL   ANALYSIS. 

tube  is  not  twisted.  There  is  of  course  a  slight  leak 
of  gas  from  the  bomb  after  N  leaves  the  nut  and 
before  R  is  closed,  but  the  time  required  for  the  half- 
turn  is  so  short  and  the  outflow  so  slow  that  the  loss 
is  insignificant.  There  is  no  need  to  Jmrry  in  this 
operation.  Be  deliberate  and  careful  of  the  apparatus. 
A  valve  like  R  is  a  nice  piece  of  workmanship,  and  to 
endure  much  usage  it  must  be  treated  with  care. 

The  bomb  is  now  ready  to  be  undamped  and  set 
into  the  ring  preparatory  to  transfer  to  the  calorimeter. 
It  can  be  left  standing  indefinitely,  but  must  be 
handled  with  caution  (best  by  lifting  with  fingers 
beneath  R,  to  avoid  spilling  the  charge). 

Preparation  of  Calorimeter. — The  outer  jacket  of 
the  calorimeter  should  be  filled  with  water  at  about 
the  room  temperature  or  a  few  degrees  higher.  If 
left  standing  from  day  to  day  it  will  usually  be  nearly 
enough  right.  It  is  well  to  stir  it  (blow  air  through 
it)  somewhat  before  beginning  work,  if  it  has  stood  for 
some  time. 

Be  sure  that  the  inner  surface  of  this  jacket,  i.e., 
the  one  which  is  next  the  calorimeter,  is  thoroughly 
dry,  and  do  not  let  any  water  spill  into  it — or  remove 
it  if  it  does  so. 

Thoroughly  dry  the  outer  surface  of  the  calorimeter 
and  keep  it  so.  Moisture  depositing  on  or  evaporating 
from  the  surface  of  the  calorimeter  is  sure  to  cause  an 
irregular  error  which  may  spoil  otherwise  good  work. 

Put  the  calorimeter  in  place.  Transfer  the  bomb  to 
it,  and  adjust  the  stirrer  so  that  it  works  properly. 

Pour  in  the  proper  amount  of  water,   about  2.25 


FUEL   ANALYSIS— HEATING    VALUE.  63 

liters,  at  a  suitable  temperature,  best  by  using  marked 
flasks  carefully  calibrated  beforehand. 

Insert  the  thermometer. 

See  that  the  electrical  attachments  are  ready  for 
instantaneous  use.  The  whole  is  then  ready  for  the 
combustion. 

Combustion  Observations. — With  apparatus  all  in 
place  run  the  stirrer  briskly  and  continuously  until 
the  completion  of  the  work.  Allow  about  five  minutes 
for  everything  to  come  to  a  normal  condition.  Then 
take  temperature  readings  to  at  least  0.01°  at  each 
quarter  minute  for  at  least  five  minutes.  Record  the 
times  (h.  m.  s.)  and  corresponding  thermometer-read- 
ings, thus: 

Remarks. 
After  5m  stirring 


Time. 

Temp. 

2h   jgm 

o9 

I5°.24 

15 

.24 

30 

•25 

45 

.25 

16 

0 

.25 

15 

.26 

30 

.26 

25 

o 

— 

15 

15.6 

30 

•9 

45 

16.2 

26 

o 

•  5 

etc. 

etc. 

Coal  ignited 


Exactly  at  the  beginning  of  a  noted  minute  close 
the  electric  circuit  through  the  fuse-wire.  If  the 
arrangements  are  right,  this  will  cause  the  coal  to 
ignite  at  once  and  the  combustion  is  almost  instan- 
taneous. Owing  to  the  time  required  to  transmit  the 


64  GAS  AND   FUEL  ANALYSIS. 

heat  through  the  bomb  to  the  water,  the  temperature, 
however,  will  continue  to  rise  for  two  or  three  minutes. 
Keep  up  the  steady  stirring  and  the  quarter-minute 
temperature-readings  for  at  least  ten  minutes  after 
ignition,  recording  as  above.  One  or  two  observations 
maybe  unavoidably  lost  before  and  after  ignition,  but 
this  does  not  materially  affect  the  results.  The  read- 
ings during  the  rapid  rise  are  also  less  close. 

As  soon  as  the  rise  begins  to  slow  down,  however, 
the  hundredths  of  a  degree  must  again  be  secured. 
This  makes  a  series  of  observations  of  15  to  20 
minutes'  duration.  The  use  of  the  readings  to  obtain 
the  cooling  correction  and  the  corrected  rise  of  tem- 
perature of  the  calorimeter  is  given  under  the  heading 
"  Cooling  Correction  "  farther  on. 

This  completes  the  observations  unless  it  is  desired 
to  test  the  character  of  the  products  of  combustion. 
The  bomb  should  now  be  opened  and  rinsed,  as  the 
nitric  acid  formed  by  the  oxidation  of  the  nitrogen  in 
the  coal  and  air  attacks  the  metallic  lining  unless  it  be 
of  gold.  Also  the  top  is  more  easily  unscrewed  at 
first  than  later.  Leave  the  top  off. 

Before  unscrewing  the  top  of  the  bomb  be  sure  to 
open  the  valve  R  to  relieve  the  presure. 

Heat  Capacity  of  Bomb  and  Calorimeter. — The 
heat  capacity  of  the  bomb  may  be  found : 

1.  From  the  weights  and  assumed  specific  heats  of 
the  parts. 

2.  By  raising  the  bomb  to  an  observed  high  tem- 
perature and  immersing  in  water,  i  e.,   by  the  usual 
"  method  of  mixtures." 

3.  By  burning  in  it  a  substance  of  known  heat  of 


FUEL  ANALYSIS— HEATING    VALUE.  65 

combustion,  such  as  pure  naphthaline,  and  calculating 
back  to  find  the  heat  capacity  of  the  bomb. 

The  first  method  is  not  reliable.  Errors  of  several 
per  cent  may  enter  in  the  assumed  specific  heats. 

The  second  method  is  very  difficult  of  exact  per- 
formance, owing  to  the  size  and  form  of  the  bomb. 

The  third  method  is  by  far  the  most  reliable,  but  of 
course  depends  on  the  correctness  of  the  assumed  heat 
of  combustion  of  the  substance  used.  That  of  naphtha- 
line has  been  so  well  determined  by  Berthelot  and 
others,*  and  the  substance  is  so  easily  and  cheaply 
obtained  in  a  pure  state,  that  dependence  can  be 
placed  on  the  results.  This  method  has  the  great 
advantage  that  it  involves  the  use  of  the  apparatus  in 
precisely  the  same  way  as  in  subsequent  determina- 
tion, so  that  any  systematic  errors  of  method  tend  to 
cancel  one  another.  It  also  determines  at  the  same 
time  the  heat  capacity  of  the  calorimeter  and  stirrer 
just  as  used. 

The  capacity  of  the  calorimeter  and  stirrer  may 
best  be  determined  in  connection  with  that  of  the 
bomb  by  the  third  method  just  described.  Otherwise 
it  may  be  found  by  the  first  method,  or  by  a  method 
similar  to  the  second,  viz.,  by  pouring  into  the  calorim- 
eter when  partly  full  water  of  a  known  temperature 
different  from  that  of  the  water  in  the  calorimeter, 
noting  all  temperatures  and  weights.  This  last 
method,  however,  is  very  unsatisfactory  in  practice 
owing  to  the  small  heat  capacity  of  the  calorimeter 
and  to  the  losses  of  heat  in  pouring  the  water,  etc. 

*  i  gram  of  naphthaline  evolves  9692  C.  This  is  the  average  of 
150  determinations  by  four  different  obervers. 


66  GAS  AND   FUEL  ANALYSIS. 

A  general  expression  for  computing  the  heat  of 
combustion  from  the  bomb  observations  is  as  follows: 
Let  n  represent  the  number  of  grams  of  combustible, 
H  the  heat  of  combustion  sought,  IV  the  weight  of 
water  in  the  calorimeter,  and  k  the  heat  capacity, 
or  water  equivalent,  of  bomb,  calorimeter,  stirrer, 
thermometer,  etc.  ;  tl  and  /a  represent  the  initial  and 
final  temperatures  of  the  water.  Then 

nH= 

whence 


This  expression  is  exact  if  ^  is  corrected  for  loss  by 
cooling  as  described  in  the  methods  for  "  Cooling 
Correction,"  p.  67. 

The  value  of  k  may  be  determined  by  either  of  the 
following  methods;  a  simplification  may,  however,  be 
introduced  which  will  save  much  labor  if  an  accuracy 
of  not  more  than  about  one  per  cent  is  sought,  pro- 
vided that  k  is  found  by  burning  naphthaline  or  other 
known  substance.  Use  enough  of  this  substance  to 
cause  about  the  same  rise,  t^  —  /,  ,  (within  i°)  as  will  be 
caused  by  one  gram  of  coal.  Omit  the  cooling  correc- 
tion entirely,  using  for  /2  the  maximum  temperature 
attained.  Then  compute  k\  this  value  will  be  erro- 
neous by  a  small  amount  owing  to  the  neglect  of  the 
correction.  Now  in  subsequent  measurements  on  coal 
also  neglect  the  cooling  correction,  using  for  /2  the 
maximum  observed  temperature  as  before,  thus  leav- 
ing an  error  in  /2.  Since  the  rise  A,  —  /,  in  both  cases 
will  be  nearly  the  same,  the  error  in  k  will  almost 


FUEL   ANALYSIS— HEATING    VALUE.  6? 

exactly  affect  that  in  /„  in  the  coal-test,  and  the  result- 
ing value  of  H  will  be  nearly  free  from  this  error. 
This  method  of  course  implies  that  W  is  nearly  con- 
stant and  that  ^  is  systematically  arranged  to  be  either 
about  at  the  air-temperature  or  a  definite  amount 
below  it,  as  described  under  "  Cooling  Correction," 
so  that  the  cooling  loss  is  about  the  same.  The  time- 
interval  from  £,  to  /„  must  for  the  same  reason  be 
nearly  constant  in  all  cases. 

Cooling  Correction. — In  all  careful  calorimetric 
work,  one  of  the  most  troublesome  sources  of  error  is 
the  loss  or  gain  of  heat  by  the  calorimeter  from  its 
surroundings.  This  loss  or  gain  is  due  to  radiation, 
to  air-convection  currents,  and  to  evaporation  or  con- 
densation. Unavoidable  irregularities  in  the  condi- 
tions and  the  smallness  of  the  quantities  to  be  measured 
render  the  amount  of  the  correction  variable  and  its 
determination  uncertain.  Many  methods  of  making 
the  correction  have  been  proposed.  One  of  the  best 
of  these  is  the  first  of  the  two  given  below,  but  the 
second,  although  a  little  more  troublesome  in  the 
execution  of  the  work,  appears  to  be  more  trustworthy 
in  its  results.  The  second  method  is  to  be  used. 

First  Method. — This  is  described  in  the  Physical 
Laboratory  Notes,  I,  under  "  Specific  Heat  of  Solids." 
In  this  method  the  water  at  the  outset  should  be  at 
such  a  temperature  that  it  is  gaining  very  slowly. 
For  an  open  calorimeter  this  is  about  i°  or  2°  below 
the  air-temperature,  but  varies  with  circumstances. 
Water  which  has  been  long  standing  in  the  room  is 
generally  about  right. 

Second  Method. — For    the    discussion    and    details 


68  GAS  AND   FUEL  ANALYSIS. 

reference  may  be  had  to  an  article  by  Professor 
Holman  in  Proc.  American  Academy  of  Arts  and 
Sciences,  1895,  p.  245;  also  in  The  Technology 
Quarterly,  8,  344. 

Berthiers  Method.  —  Another  method  of  direct 
determination  was  proposed  by  Berthier  in  1835.* 
It  uses  as  a  measure  of  the  heating  value  the  amount 
of  lead  which  a  fuel  would  reduce  from  the  oxide;  in 
other  words,  it  is  proportional  to  the  amount  of  oxygen 
absorbed. 

The  method  is  as  follows:  Mix  one  gram  of  the  fine 
dry  coal  with  from  2O  to  40  grams  of  oxychloride  and 
oxide  of  lead,  cover  with  20  grams  of  oxide  of  lead 
(litharge),  heat  to  redness  in  a  crucible,  and-weigh  the 
lead  button  formed.  One  part  of  carbon  is  equivalent 
to  34  parts  of  lead  (or  235  calories  C). 

While  this  method  of  course  can  make  no  preten- 
sions to  scientific  accuracy,  yet  the  results  seem  as 
trustworthy  as  those  obtained  by  calculation  accord- 
ing to  Dulong's  formula  (see  £,  below),  and  it  is  readily 
applicable. 

b.  Determination  of  Heating  Value  by  Calculation. 

The  method  of  determination  of  the  heating  value 
first  described,  though  exact,  has  the  disadvantages 
that  the  apparatus  is  costly  and  the  compressed 
oxygen  is  not  easily  obtained.  To  obviate  these, 
it  has  been  sought  to  obtain  the  heating  value  by 
calculation  from  the  chemical  analysis,  the  heating 
value  of  the  constituents  being  known.  This  has 
the  disadvantage  that  we  have  no  absolute  knowl- 

*  Dingler's  Polytechnisches  Journal,  58,  391. 


FUEL  ANALYSIS-HEATING    VALUE.  69 

edge — nay,  not  even  an  approximate  idea — as  to  how 
the  carbon,  hydrogen,  water,  and  sulphur  exist  in  the 
coal,  so  that  any  formula  must  of  necessity  be  quite 
removed  from  the  truth.  Dulong  was  the  first  to 
propose  the  method  by  calculation,  and  his  formula  is 

Soooc  +  34500^  —  \d) 
~T5o~ 

c,  h,  and  o  representing  the  percentages  of  carbon, 
hydrogen,  and  oxygen  in  the  coal. 

Many  modifications  of  this,  considering  the  water 
formed,  the  heat  of  vaporization  of  carbon,  or  the 
volatile  hydrocarbons,  have  been  proposed. 

Bunte  *  finds  that  the  following  formula  gives  results 
varying  from  -|-  2.8  to  —  3.7  per  cent: 

/         o  \ 
8080^  +  28800/2  —  o     +  2500.?  —  6oow 

\  o  / 

IOO 

s  and  w  represent  the  percentages  of  sulphur  and 
water  respectively.  It  is,  however,  inapplicable  to 
anthracite  coal.  It  would  scarcely  seem  that  the 
sulphur  would  be  worth  considering  unless  high,  one 
per  cent  affecting  the  result  but  0.3  per  cent. 
Mahler  employs  the  formula 

8140^7+  34500/2  —  3000(0  +  n) 
100 

o  and  n  representing  oxygen  and  nitrogen,  and  states 
that  it  gives  results  within  3  per  cent. 

The  results  obtained  by  these  formulae  for  anthracite 
coal  are  as  a  rule  considerably  too  low. 

*  Jour.  fUr  Gasbeleuchtung,  34,  21-26  and  41-47. 


?O  GAS  AND   FUEL   ANALYSIS. 

CALORIFIC   POWER   OF   GASEOUS    FUEL. 

a.  Direct  Determination. 

Perhaps  the  best  apparatus  for  the  determination  of 
the  heating  value  of  gases  is  the  Junker  calorimeter, 
Figs.  1 6  and  17.  The  following  description  is  taken 


FIG.  16. — JUNKER  GAS  CALORIMETER  (SECTION). 

from  an  article  by  Kuhne  in  the  Journal  of  the  Society 
of  Chemical  Industry,   vol.    14,   p.   631.     As  will  be 


FUEL   ANALYSIS— HEATING    VALUE.  71 

seen  from  Fig.  16,  this  consists  of  a  combustion-cham- 
ber, 28,  surrounded  by  a  water-jacket,  15  and  16, 
this  being  traversed  by  a  great  many  tubes.  To 
prevent  loss  by  radiation  this  water-jacket  is  sur- 


FIG.  17.— JUNKER  GAS  CALORIMETER. 

rounded  by  a  closed  annular  air-space,  13,  in  which 
the  air  cannot  circulate.  The  whole  apparatus  is 
constructed  of  copper  as  thin  as  is  compatible  with 
strength.  The  water  enters  the  jacket  at  i,  passes 
down  through  3,  6,  and  7,  and  leaves  it  at  21,  while 


72  GAS  AND    FUEL    ANALYSIS. 

the  hot  combustion-gases  enter  at  30  and  pass  downr 
leaving  at  31.  There  is  therefore  not  only  a  very 
large  surface  of  thin  copper  between  the  gases  and  the 
water,  but  the  two  move  in  opposite  directions,  during 
which  process  all  the  heat  generated  by  the  flame  is 
transferred  to  the  water,  and  the  waste  gases  leave  the 
apparatus  approximately  at  atmospheric  temperature. 
The  gas  to  be  burned  is  first  passed  through  a  meter, 
Fig.  17,  and  then,  to  insure  constant  pressure,  through 
a  pressure-regulator.  The  source  of  heat  in  relation 
to  the  unit  of  heat  is  thus  rendered  stationary;  and  in 
order  to  make  the  absorbing  quantity  of  heat  also 
stationary,  two  overflows  are  provided  at  the  calo- 
rimeter, making  the  head  of  water  and  overflow  con- 
stant. The  temperatures  of  the  water  entering  and 
leaving  the  apparatus  can  be  read  by  12  and  43;  as 
shown  before,  the  quantites  of  heat  and  water  passed 
through  the  apparatus  are  constant.  As  soon  as  the 
flame  is  lighted,  43  will  rise  to  a  certain  point  and  will 
remain  nearly  constant. 

Manipulation. — The  calorimeter  is  placed  as  shown 
in  Fig.  17,  so  that  one  operator  can  simultaneously 
observe  the  two  thermometers  of  the  entering  and 
escaping  water,  the  index  of  the  gas-meter,  and  the 
measuring-glasses. 

No  draft  of  air  must  be  permitted  to  strike  the  ex- 
haust of  the  spent  gas. 

The  water-supply  tube  w  is  connected  with  the 
nipple  a  in  the  centre  of  the  upper  container;  the 
other  nipple,  b,  is  provided  with  a  waste-tube  to  carry 
away  the  overflow,  which  latter  must  be  kept  running 
while  the  readings  are  taken. 


FUEL   ANALYSIS— HEATING    VALUE.  73 

The  nipple  c  through  which  the  heated  water  leaves 
the  calorimeter  is  connected  by  a  rubber  tube  with 
the  large  graduate,  d  empties  the  condensed  water 
into  the  small  graduate. 

The  thermometers  being  held  in  position  by  rubber 
stoppers  and  the  water  turned  on  by  e  until  it  dis- 
charges at  c,  no  water  must  issue  from  d  or  from  39, 
Fig.  16,  as  this  would  indicate  a  leak  in  the  calorim- 
eter. 

The  cock  e  is  now  set  to  allow  about  two  liters  of 
water  to  pass  in  a  minute  and  a  half,  and  the  gas 
issuing  from  the  burner  ignited.  Sufficient  time  is 
allowed  until  the  temperature  of  the  inlet-water 
becomes  constant  and  the  outlet  approximately  so; 
the  temperature  of  the  inlet-water  is  noted,  the  read- 
ing of  the  gas-meter  taken,  and  at  this  same  time  the 
outlet-tube  changed  from  the  funnel  to  the  graduate. 
Ten  successive  readings  of  the  outflowing  water  are 
taken  while  the  graduate  (2-liter)  is  being  filled  and 
the  gas  shut  off. 

EXAMPLE. — Temp,  of  incoming  water,  17.2° 

"   outgoing       "  43.8° 

Increase,  26.6° 
Gas  burned,  0.35  cu.  ft. 

liters  water  X  increase  of  temp.    _  2  X  26.6 
cu.  ft.  gas  0.35 

=  152. 3C. 

From  burning  one  cubic  foot  of  gas  27.25  cc.  of 
water  were  condensed.  This  gives  off  on  an  average 
0.6  C.  per  cc. 


74  GAS  AND   FUEL   ANALYSIS. 

27.25  X  0.6  =  16.30; 
152.3  —  16.3  =  136  C  per  cubic  foot; 
136  X  3.96828  =  540  B.T.U. 

The  apparatus  has  been  tested  for  three  months 
in  the  German  Physical  Technical  Institute  with  hy- 
drogen, with  but  a  deviation  of  0.3  per  cent  from 
Thomson's  value.  This  value  may  vary  nearly  that 
amount  from  the  real  value  owing  to  the  method 
which  he  employed. 

b.  By  Calculation. 

Oftentimes  it  may  be  impracticable  to  determine 
the  heating  value  of  gases  directly;  in  such  cases 
recourse  must  be  had  to  the  calculation  of  its  calorific 
power  from  volumetric  analysis  of  the  gas. 

To  this  end  multiply  the  percentage  of  each  con- 
stituent by  its  number  as  given  in  Table  IV,  and  the 
sum  of  the  products  will  represent  the  British  Thermal 
Units  evolved  by  the  combustion  of  one  cubic  foot  of 
the  gas.*  It  is  assumed  that  the  temperature  of  the 
gas  burned  and  the  air  for  combustion  is  60°  F.,  and 
that  of  the  escaping  gases  is  328°  F.,  that  correspond- 
ing to  the  temperature  of  steam  at  100  pounds  abso- 
lute pressure. 

As  has  been  already  stated,  column  3  in  Table  IV 
is  based  upon  the  assumption  that  the  gas,  and  air  for 
its  combustion,  enter  at  60°  F.,  and  the  products 
of  combustion  leave  at  328°  F. ;  in  column  4  it  is 
assumed  that  the  entering  temperature  of  both  gas 
and  air  is  32°  F.,  and  the  combustion-gases  are  cooled 

*  H.  L.  Payne,  Jour.  Analytical  and  Applied  Chem.,  7,  230. 


FUEL  ANALYSIS— HEATING    VALUE.  75 

to  32°  F.  In  case  these  conditions  are  varied,  the 
amount  of  heat  which  the  gas  and  air  bring  in  must  be 
determined;  this  is  found  in  the  usual  way  by  multi- 
plying the  proportionate  parts  of  I  cubic  foot,  as 
shown  by  the  analysis,  by  the  specific  heat  of  the  gas, 
and  this  by  the  rise  in  temperature  (difference  between 
observed  temperature  and  32°  F.).  The  quantity  of 
air  necessary  for  combustion  is  found  by  multiplying 
the  percentage  composition  of  the  gas  by  the  number 
of  cubic  feet  necessary  for  the  combustion  of  each 
constituent. 

An  example  will  serve  to  make  this  clear.  The 
analysis  of  Boston  gas  is  as  follows:* 

CO2       "Illuminants."  O  CO  CH4  H  N 

2.9  15.0  o.o        25.3        25.9        27.9        3.0 

Or  in  one  cubic  foot  there  are 

.029  C02 259  CH4 

.150  "  illuminants" 279  H 

.25300 030  N 

Let  us  suppose  its  temperature  is  62°  F.  The 
quantity  of  heat  which  one  cubic  foot  of  the  gas  brings 
in  is  then  the  sum  of  the  heats  of  its  constituents; 
this  latter  is  its  volume  X  volumetric  specific  heat  X 
rise  in  temperature. 

The  "  volumetric  "  specific  heat  is  the  quantity  of 
heat  necessary  to  raise  one  cubic  foot  of  the  gas  from 
32°  to  33°  F. ;  these  are  given  in  the  Appendix, 
Table  II. 

*  Jenkins,  Annual  Report  Inspector  of  Gas  Meters  and  Illumi- 
nating Gas,  1896,  p.  ii, 


?  GAS  AND    FUEL  ANALYSIS. 

Vol.          Vol.  Sp.  Ht.       Rise. 

"  Illuminants"  =  o.  15     X  0.04    X  0.30  .18  B.T.U. 

CO  =0.253x0.019X0.30  .14 

CH4  =0.259X0.027x0.30  .21 

H  =0.279X0.019X0.30  .16 

COaN  insignificant. 


Total  heat  brought  in  by  gas. ...  0.69  B.T.U. 

The  quantity  of  air  necessary  to  burn  these  several 
gases  is,  Table  III: 

"  Illuminants" 0.15     X  14.34=2.15 

CO 253  X     2.39=     .60 

CH4 259  X     9-56  =  2.48 

H 279  X     2.39=     .67 


Theoretical  quantity  of  air 5.90  cu.  ft. 

Add  20  per  cent  excess 1 .20 

Quantity  of  air  used  in  burning  I  cubic 

foot  of  Boston  gas .  . 7. 10  cu.  ft. 

Assume  its  temperature  to  be  72°  F. ;  then  the 
heat  it  brings  in  is 

7.1  X  .019  X  0.40  =  5.4  B.T.U. 
Total  gain  is  5.4  +  0.7  =  6.1  B.T.U. 

Assume  further  that  the  gases,  instead  of  passing 
out  at  a  temperature  of  328°  F.,  leave  at  the  same 
temperature  as  that  of  the  chimney-gases,  p.  29,  250° 
C.  or  482°  F. 

The  calculation  of  the  heat  carried  away  is  similar 
to  that  there  given. 


FUEL   ANAL  Y  SIS-HE  A  TINGT^LG^T  77 

0.15    cu.   ft.  of  lt  illuminants  "  produces,  Table   III, 

0.3  cu.  ft.  CO2  and  0.3  cu.  ft.  steam; 
0.253  cu.  ft.  of  carbonic  oxide  produces  .253  cu.  ft. 

C02; 
0.259  cu.  ft.  methane  produces  0.259  cu-  ft-  CO2  and 

.518  cu  ft.  steam; 
0.279  cu-  ft-  hydrogen  produces  .279  cu.  ft.  steam. 

From  the  combustion  of  the  gas  there  results  .812 
cu.  ft.  CO2 ,  1.097  cu.  ft.  steam,  and  5.90  X  79.08  or 
4.665  cu.  ft.  N. 

The  quantity  of  heat  they  carry  off  is  as  follows : 

Vol.  Vol.  Sp.  Ht.  Rise.  B.T.U. 

CO2 812  X  .027    X    450=  9-9 

N 4.66    X  .019    X    450=  39-9 

Excess  of  air. .    1.2       X  .019    X    450  =  10.2 

Steam „ 1.097  X  .0502  X  1229=  67.7 


Total  heat  lost =     127.7 

The  loss  due  to  the  steam  is  found  by  multiplying 
the  weight  of  steam  found  by  the  "  Total  Heat  of 
Steam,"  as  found  from  Steam  Tables.*  The  tables, 
however,  do  not  extend  beyond  428°  F. ;  it  can  be 
calculated  by  the  formula 

Total  heat  =  A  =  1091.7  +  0.305^  —  32). 

One  cubic  foot  of  hydrogen  when  burned  yields 
.0502  Ibs.  of  water. 

The  heat  generated  by  the  combustion  of  the  gas  is 
found  by  multiplying  its  volume  by  its  calorific  power, 
Table  IV. 

*  Peabody's  Steam  Tables, 


78  GAS  AND   FUEL   ANALYSIS. 

li  Illuminants" 0.15     X  2000.0  =  300.0  B.T.U. 

CO 0.253  x    341-2=    86.3 

CH4 0.259  x  1065.4=276.0 

H 0.279  X     345-4=    96-3 


Heat  generated  by  the  gas. 758.6  B.T.U, 

Heat    gained    by  rise    in    temperature 

of    entering    gas    (62°  F.)    and    air       6.1 

(72°F.) 

764.7 
Total  heat  lost 127.7 


637.0  B.T.U. 

This  figure,  637  B.T.U.,  represents  the  heating 
power  of  one  cubic  foot  of  the  gas  measured  at  62°  F., 
and  is  consequently  too  large;  its  heating  value  at 
32°  F.  is  represented  by 

X  637,  or  600.3  B.T.U. 


492  +  30 


APPENDIX. 


TABLE   I. 

TABLE  SHOWING  THE  TENSION  OF  AQUEOUS  VAPOR  AND  ALSO  THE 
WEIGHT  IN  GRAMS  CONTAINED  IN  A  CUBIC  METER  OF  AIR 
WHEN  SATURATED. 

From  5°  to  30°  C. 


Temp. 

Tension, 
mm. 

Grams. 

Temp. 

Tension, 
mm. 

Grams. 

Temp. 

Tension, 
mm. 

Grams. 

5 

6.5 

6.8 

14 

ii.  9 

12.0 

23 

20,9 

20.4 

6 

7.0 

7-3 

15 

12.7 

12.8 

24 

22.2 

21-5 

7 

7-5 

7-7 

16 

13-5 

13-6 

25 

23.6 

22.9 

8 

8.0 

8.1 

17 

14.4 

14-5 

26 

25.0 

24.2 

9 

8.5 

8.8 

18 

15-4 

15-1 

27 

26.5 

25.6 

10 

9.1. 

9.4 

19 

16.3 

16.2 

28 

28.1 

27.0 

ii 

9-8 

IO.O 

20 

17.4 

17.2 

29 

29.8 

28.6 

12 

10.4 

10.6 

21 

18.5 

18.2 

30 

31-5 

29.2 

13 

II.  I 

n-3 

22 

19.7 

19-3 

TABLE   II. 

"  VOLUMETRIC  "    SPECIFIC   HEATS    OF   GASES.* 

Air 0.019  "  Illuminants  " 0.040 

Carbon  dioxide 0.027  Methane 0.027 

Carbonic  oxide 0.019  Nitrogen 0.019 

Hydrogen 0.019  Oxygen 0.019 

The  "  volumetric"  specific  heat  is  the  quantity  of  heat  neces- 
sary to  raise  the  temperature  of  one  cubic  foot  of  gas  from  32°  F. 
to  33°  F. 

*  H.  L.  Payne,  four.  AnaL  and  Applied  Chem.,  7,  233. 

79 


8o 


APPENDIX. 


TABLE   III. 

THE  VOLUME  OF  OXYGEN  AND  AIR  NECESSARY  TO  BURN  ONE  CUBIC 
FOOT  OF  CERTAIN  GASES,  TOGETHER  WITH  THE  VOLUME  OF 
THE  PRODUCTS  OF  COMBUSTION. 


Name. 

Formula. 

Volume  of 
Oxygen. 

Volume* 
of  Air. 

Volume  of 
Steam. 

Volume  of 
Carbon 
Dioxide. 

Hydrogen  
Carbonic  oxide. 
Methane  

H2 
CO 
CH4 

0-5 
0-5 
2.O 

2-39 
2-39 

Q.  C6 

I 
O 
2 

O 
I 
j 

C«H« 

3e 

16  T\ 

2 

CoHs 

5O 

2<J    no 

CTJ 

6  *, 

•3  j    o7 

8.0 

38.24 

6 

e 

Hexane       .    . 

C«H,i 

Q.  % 

4C  .  A  I 

7 

6 

Ethylenef   ... 

3.  0 

14  •  Id 

2 

2 

PropyleneJ  .... 
Benzene^  

C3H6 
C6H6 

4-5 
7.  5 

21.51 

qc  .8s 

3 

•2 

3 
6 

*  Air  being  20.92  per  cent   by  volume,  4.78   volumes   contain 
I  volume  of  oxygen. 

f  The  chief  constituent  of  "  illuminants,"  new  name  "  ethene." 
J  New  name  "  propene." 
§  Often  called  benzol,  not  to  be  confounded  with  benzene. 


TABLES. 
TABLE   IV. 


8l 


CALORIFIC    POWER   OF   VARIOUS    GASES*  IN   BRITISH   THERMAL   UNITS 
PER    CUBIC    FOOT. 


Name. 

Symbol. 

60°  initial. 
328°  final. 

32°  initial. 
32°  final. 

H 

26"?  .  2 

VAC.  .A 

Carbonic  oxide  

CO 

3O6.Q 

04.1  .2 

CH4 

Ss^.o 

1065.0 

I7OO.O 

2OOO.O 

C-jH6 

1861  o 

C3H8 

26^7  .O 

Butane     .                ... 

QJ.J.  i  .  o 

Pentane      

C  H 

4.2^  .O 

Hexanet           

C6Hi4 

COI7  .O 

C2H4 

1674.  o 

C3H6 

25OQ  .O 

C6Ha 

40  I  2  .  O 

*  H.  L.  Payne,  loc.  cit. 

f  Where  the  "  illuminants  "  are  derived  chiefly  from  the  decom- 
position of  mineral  oil. 

\  The  chief  constituent  of  the  "gasolene"  used  in  the  gas 
machines  for  carburetting  air. 


TABLE   V. 

SHOWING  THE  WEIGHT  OF  A  LITER  AND  SPECIFIC  GRAVITY  REFERRED 
TO    AIR,    OF    CERTAIN    GASES  AT   O°    C.    AND    760    MM. 


Name  of  Gas. 

Weight,  Grams. 

Specific  Gravity. 

Carbon  dioxide.      .  .  . 

i  .^51 
I   966 

•9U7 

Hydrogen  

o  0806 

•  519 

Methane  .. 

O7l  C 

I    2^  ^ 

I  .  d^O 

I     IO^ 

Air  

82 


TABLE   VI. 

SOLUBILITY   OF   VARIOUS    GASES    IN   WATER. 

One  volume  of  water  at  20°  C.  absorbs  the  following  volumes  of 
gas  reduced  to  o°  C.  and  760  mm.  pressure. 


Name  of  Gas. 

Symbol. 

Volumes. 

Carbonic  oxide  

CO 
CO2 
Ha 
CH4 

N2 
02 

0.023 
0.901 
0.019 
0.035 
0.014 
0.028 
0.017 

Air                                            

TABLE   VII. 


MELTING-POINTS    OF    VARIOUS    METALS    AND    SALTS,    FOR   USE   WITH 
APPARATUS    FIG.    II. 

(From  Carnelley  Melting-  and  Boiling-point  Tables.) 


Alphabetically. 

Aluminium 660°  C.* 

Antimony 432 

f  Barium  chloride. ...  860 

Bismuth 268 

f  Calcium  fluoride. ...  902 

Cadmium 320 

fCadmium  chloride. .  541 

Copper 1095 

Lead 334 

fPotassium  chloride..  734 

fSodium  chloride. ...  772 

Tin 233 

Zinc 433 


By  Temperatures. 

Tin 233'C. 

Bismuth 268 

Cadmium 320 

Lead 334 

Antimony 432 

Zinc 433 

Cadmium  chloride. ...  541 

Aluminium 660* 

Potassium  chloride. . .  734 

Sodium  chloride 772 

Barium  chloride 860 

Calcium  fluoride 902 

Copper 1095* 


*  Holman,  Proc.  Am.  Academy,  31,  218. 

f  These  salts  must  be  dried  at  105°  C.  to  constant  weight. 


TABLES.  S3 

TABLE   VIII. 

GIVING    THE    NUMBER    OF    TIMES    THE    THEORETICAL   QUANTITY   OF 
AIR   SUPPLIED,    WITH   VARIOUS    GAS   ANALYSES.* 


CO-j-0 

N  =  79- 

COa-i-O+CO=2i 

N  =  8o. 
CO2-!-O+CO=2o. 

N  =  81. 
COa+0+CO=i9. 

N  =  82. 
CO2-j-0+CO=i8. 

21 

.00 

20 

.05 

.00 



.... 

19 

.10 

•05 

I.OO 

.... 

18 

•  17 

.10 

•05 

.00 

17 

•  23 

.16 

.10 

•05 

16 

•  31 

•23 

.16 

.10 

15 

.40 

-3i 

•  23 

.16 

14 

•  50 

•39 

•30 

.22 

13 

.61 

•49 

.39 

•30 

12 

•75 

i.  60 

.48 

•38 

II 

.91 

1-73 

•59 

•47 

IO 

2.10 

1.89 

•72 

•58 

9 

2-33 

2.07 

•87 

•70 

8 

2.62 

2.29 

2.04 

•85 

7 

3.00 

2-57 

2.26 

2.02 

6 

3-50 

2.92 

2.52 

2.23 

5 

4.20 

3-39 

2.86 

2.48 

4 

5.25 

4-05 

3-30 

2.79 

3 

7.00 

5-oo 

3-89 

3.2O 

2 

10.50 

6.53 

4.76 

3.76 

I 

21  .OO 

9-43 

6.10 

4-54 

Coxe,  Proc.  N.  E.  Cotton  Manufacturers'  Assoc.,  1895. 


TABLE   IX. 

COMPARISON    OF   METRIC   AND    ENGLISH    SYSTEMS,, 

I  cubic  inch  =  16.39  c.c. 

i  cubic  foot  =  28.315  liters, 

i  Imperial  gallon  =    4-543      " 


I  Ib.  avoirdupois  =  453-593  grams. 

I  calorie  =      3.969  B.T.U.  (Rontgen). 


INDEX. 


PAGE 

Acid  hydrochloric,  reagent 34 

Air-pumps,  Bunsen's 7 

,  Richards' 7 

,  steam 9 

Anthracite  coal,  analysis  of 45 

Aqueous  vapor,  table  of  tension  of 79 

,   specific  heat 29 

Aspirator 9 

,  Muencke's 38 

Bagasse  calorific  power 47 

Benzophenon,  boiling-point 25 

Berthier's  method  of  determining  calorific  power  of  coal 68 

Bituminous  coal,  analysis  of 44 

,  varieties 43 

Blast-furnace  gas,  analysis  of 48 

Boiling-point  of  various  substances 25 

Brown  coal 43 

,  analysis  of 43 

Bunte's  gas  apparatus 16 

Calculations 27 

Calorimeters  of  Barrus 56 

Fischer 56 

Hempel 57 

Mahler 57 

Thompson,  L 56 

Thomson,  W 56 

Carbon  dioxide,  determination  of 13,  18,  21 

,  specific  heat 29 

85 


86  INDEX. 

PAGE 

Carbonic  oxide,  determination  of 14,  19,  22 

,  loss  due  to  formation  of 32 

,  specific  heat 29 

Charcoal,  analysis  of 45 

,  preparation 45 

Coal,  air  required  for  combustion 45 

,  calorific  power 45 

,  formation  of 42 

,  method  of  analysis 50 

Coal-gas,  analysis  of 49 

,  calorific  power 49 

Coke,  analysis  of 46 

,  determination  of 50 

,  preparation 46 

Cooling  correction  in  calorimetry 67 

Course  in  gas  analysis 39 

Cuprous  chloride  acid,  reagent 34 

,  ammoniacal,  reagent 35 

Elliott's  gas  apparatus 20 

Formulae,  Bunte's,  for  calorific  power  of  coal 69 

,  Dulong's,  for  calorific  power  of  coal 69 

,  Lunge's,  for  heat  passing  up  chimney 32 

,  for  heat  of  combustion  with  Mahler  bomb 66 

,  Mahler's,  for  calorific  power  of  coal 69 

,  Ratio  of  air  used  to  that  theoretically  necessary. . .  31 

Fuel,  determination  of  calorific  power 56,  70 

,  loss  due  to  unconsumed 33 

Fuels,  method  of  analysis  of:  ash 55 

carbon 51 

coke  and  volatile  matter .  50 

hydrogen 51 

moisture  50 

nitrogen 55 

oxygen 56 

sulphur 55 

Gas  calorimeter,  Junker's 70 

,  determination  of  calorific  power  by  calculation 74 


INDEX.  87 

PAGE 

Gas  laboratory,  arrangement  of 37 

Generator  gas,  see  Producer-gas. 

Hydrocarbons,  determination  of 14,  23 

Illuminating  gas,  manufacture 49 

,  Boston,  analysis  of 75 

,  calorific  power  (calculated) 78 

Iron  tubes,  action  of  uncooled  gases  upon 2 

Junker's  gas  calorimeter 70 

Laboratory,  arrangement  of 37 

Lead,  quantity  reduced,  a  measure  of  the  calorific  power. ...  68 

Lignite 43 

Lunge's  method  for  determining  quantity  of  heat  passing  up 

chimney 31 

Mahler  bomb 57 

Melting-point  boxes 26 

Melting-point  of  various  substances 81 

Moisture  in  coal,  determination  of 50 

Naphthalene,  boiling-point 25 

.calorific  power 65 

Natural  gas,  analysis  of 48 

,  calorific  power 49 

Nitrogen,  determination  of,  in  coal 55 

,  gases 14 

,  specific  heat 29 

Orsat's  gas  apparatus n 

Oxygen,  determination  of,  in  coal 56 

,  gases 14,  19,  22 

,  specific  heat 29 

Peat,  analysis  of 41 

,  calorific  power 42 

,  formation 41 

,  moisture  in 41 

Petroleum,  formation  of , 47 


88  INDEX. 


Petroleum,  crude,  analysis  of 47 

,  calorific  power 47 

Potassium  hydrate,  reagent 36 

pyrogallate,  reagent 36 

"  Pounds  of  air  per  pound  of  coal  " 27 

Producer  gas,  analysis  of 48 

,  calorific  power 49 

Pyrometer,  Le  Chatelier's  thermoelectric , 25 

Quantity  of  heat  passing  up  chimney 28,  31 

Ratio  of  air  used  to  that  theoretically  necessary 31 

Sampling  apparatus 3,  6 

gases,  method  of 2 

,  tubes  for 2 

solid  fuels,  method  of 50 

Semi-bituminous  coal,  analysis  of » 44 

Sodium  hydrate,  reagent 36 

pyrogallate,  reagent 37 

Specific  heat  of  various  gases 29 

Spent  tan-bark,  calorific  power 46 

Sulphur,  boiling-point 25 

Table  of  quantity  of  air  necessary  to  burn  gases 80 

tension  of  aqueous  vapor 79 

weight  of  aqueous  vapor  in  air 79 

calorific  power  of  gases 81 

solubility  of  gases 82 

specific  gravity  of  gases 81 

volumetric  specific  heats  of  gases 79 

weights  of  gases 81 

melting-points  of  metals  and  salts 82 

metric  and  English  systems 83 

theoretical  quantity  of  air  supplied 83 

Temperature  measurement  of 24 

Thermometers 24 

,  testing  of 25 

Tubes  for  sampling , 2 

Volatile  matter,  determination  of ,..,..,..,.., 50 


INDEX.  89 


Water-gas,  analysis  of 48 

,  calorific  power 49 

Wheat  straw,  calorific  power 46 

Wood,  analysis  of 41 

,  calorific  power 41 

,  moisture  in   40 


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Anthony  and  Brackett's  Text-book  of  Physics 8vo,  4  00 

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Michie's  Wave  Motion  Relating  to  Sound  and  Light, 8vo,  4  00 

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Holman's  Precision  of  Measurements 8vo,  2  00 

Tillman's  Heat. 8vo,  1  50 

Gilbert's  De-magnete.     (Mottelay.) 8vo,  2  50 

Benjamin's  Voltaic  Cell 8vo,  3  00 

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ENGINEERING. 

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*  Trautwine's  Cross-section Sheet,  25 

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*  "            Excavations  and  Embankments Svo,  2  00 

*  "            Laying  Out  Curves 12ino,  morocco,  2  50 

Hudson's  Excavation  Tables.    Vol.  II 8vo,  1  00 

6 


Searles's  Field  Engineering l2mo,  morocco  flaps,  $3  00 

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Gore's  Elements  of  Goodesy 8vo,  2  50 

Wellington's  Location  of  Railways 8vo,  5  00 

*  Dredge's  Penn.  Railroad  Construction,  etc.  . .  Folio,  half  mor.,  20  00 
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Johnson's  Theory  and  Practice  of  Surveying 8vo,  4  00 

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Bridge  Trusses 8vo,  250 

Arches  in  Wood,  etc 8vo,  2  50 

Church's  Mechanics  of  Engineering— Solids  and  Fluids ....  8vo,  6  00 

"        Notes  and  Examples  in  Mechanics 8vo,  2  00 

Howe's  Retaining  Walls  (New  Edition.) 12mo,  1  25 

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"       Surveying  Instruments 12mo,  3  00 

Warren's  Stereotomy— Stone  Cutting 8vo,  2  50 

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Kirkwood's  Lead  Pipe  for  Service  Pipe 8vo,  1  50 

Wolff's  Windmill  as  a  Prime  Mover 8vo,  3  00 

Howard's  Transition  Curve  Field-book 12mo,  morocco  flap,  1  50 

Crandall's  The  Transition  Curve 12mo,  morocco,  1  50 

7 


Crandall's  Earthwork  Tables  , 8vo,  $1  50 

Pattou's  Civil  Engineering , ,8vo,  7  50 

"       Foundations 8vo,  500 

Carpenter's  Experimental  Engineering 8vo,  6  00 

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Black's  U.  S.  Public  Works 4to,  5  00 

Merriman  and  Brook's  Handbook  for  Surveyors. .  .  .12mo,  mor.,  2  00 

Merriman's  Retaining  Walls  and  Masonry  Dams 8vo,  2  00 

"          Geodetic  Surveying 8vo,  2  00 

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Weisbach's  Hydraulics.     (Du  Bois.) 8vo,  5  00 

Merriman's  Treatise  on  Hydraulics. 8vo,  4  00 

Ganguillet&  Kutter'sFlow  of  Water.  (Hering&  Trautwine.).8vo,  4  00 

Nichols's  Water  Supply  (Chemical  and  Sanitary) 8vo,  2  50 

Wolff's  Windmill  as  a  Prime  Mover 8vo,  3  00 

Ferrel's  Treatise  on  the  Winds,  Cyclones,  and  Tornadoes. .  .8vo,  4  00 

Kirkwood's  Lead  Pipe  for  Service  Pipe 8vo,  1  50 

Ruffner's  Improvement  for  Non-tidal  Rivers 8vo,  1  25 

Wilson's  Irrigation  Engineering 8vo,  4  00 

Bovey 's  Treatise  on  Hydraulics 8vo,  4  00 

Wegmann's  Water  Supply  of  the  City  of  New  York 4to,  10  00 

Hazen's  Filtration  of  Public  Water  Supply 8vo,  2  00 

Mason's  Water  Supply — Chemical  and  Sanitary 8vo,  5  00 

Wood's  Theory  of  Turbines , 8vo,  2  50 

MANUFACTURES. 

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Metcalfe's  Cost  of  Manufactures 8vo,  5  00 

Metcalf 's  Steel  (Manual  for  Steel  Users). 12nao,  2  00 

Allen's  Tables  for  Iron  Analysis 8vo,  3  00 

8 


West's  American  Foundry  Practice l2mo,  $2  50 

"      Moulder's  Text-book   .., 12mo,  250 

Spencer's  Sugar  Manufacturer's  Handbook 12mo,  inor.  flap,  2  00 

Wiechmann's  Sugar  Analysis 8vo,  2  50 

Beaumont's  Woollen  and  Worsted  Manufacture 12mo,  1  50 

*  Reisig's  Guide  to  Piece  Dyeing 8vo,  25  00 

Eissler's  Explosives,  Nitroglycerine  and  Dynamite 8vo,  4  00 

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Ford's  Boiler  Making  for  Boiler  Makers 18mo,  1  00 

Thurston's  Manual  of  Steam  Boilers 8vo,  5  00 

Booth's  Clock  and  Watch  Maker's  Manual 12mo,  2  00 

Holly's  Saw  Filing 18mo,  75 

Svedelius's  Handbook  for  Charcoal  Burners 12mo,  1  50 

The  Lathe  and  Its  Uses 8vo,  600 

Woodbury's  Fire  Protection  of  Mills 8vo,  2  50 

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"           "       "           "        Supplement 12mo,  250 

"        Encyclopaedia  of  Founding  Terms 12mo,  3  00 

Bouvier's  Handbook  on  Oil  Painting 12mo,  2  00 

Steven's  House  Painting 18mo,  75 

MATERIALS  OF  ENGINEERING. 

STRENGTH — ELASTICITY — RESISTANCE,  ETC. 

Thurston's  Materials  of  Engineering 3  vols.,  8vo,  8  00 

Vol.  I.,  Non-metallic. 8vo,  200 

Vol.  II.,  Iron  and  Steel 8vo,  3  50 

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Thurston's  Materials  of  Construction 8vo,  5  00 

Baker's  Masonry  Construction 8vo,  5  00 

Lanza's  Applied  Mechanics 8vo,  7  50 

"        Strength  of  Wooden  Columns 8vo,  paper,  50 

Wood's  Resistance  of  Materials 8vo,  2  00 

Weyrauch's  Strength  of  Iron  and  Steel.    (Du  Bois.) 8vo,  1  50 

Burr's  Elasticity  and  Resistance  of  Materials 8vo,  5  00 

Merriinan's  Mechanics  of  Materials 8vo,  4  00 

Church's  Mechanic's  of  Engineering — Solids  and  Fluids 8vo,  6  00 

9 


Crehore's  Mechanics  of  the  Girder 8  vo,  $5  00 

MacCord's  Kinematics 8vo,  5  00 

Thurston's  Friction  and  Lost  Work 8vo,  3  00 

The  Animal  as  a  Machine 12rno,  1  00 

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Warren's  Machine  Construction 2  vols.,  8vo,  7  50 

Chordal's  Letters  to  Mechanics ]  2mo,  2  00 

The  Lathe  and  Its  Uses 8vo,  6  00 

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Du  Bois's  Mechanics.     Vol.  I.,  Kinematics 8vo,  3  50 

Vol.  II.,  Statics 8vo,  400 

Vol.  III.,  Kinetics 8vo,  3  50 

Dredge's     Trans.     Exhibits     Building,      World     Exposition, 

4to,  half  morocco,  15  00 

Flather's  Dynamometers 12rno,  2  00 

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Metcalfe's  Cost  of  Manufactures 8vo,  5  00 

Benjamin's  Wrinkles  and  Recipes 12mo,  2  00 

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METALLURGY. 

IRON — GOLD— SILVER — ALLOYS,  ETC. 

Egleston's  Metallurgy  of  Silver 8vo,  7  50 

Gold  and  Mercury .8vo,  750 

"  Weights  and  Measures,  Tables 18ino,  75 

"  Catalogue  of  Minerals 8vo,  2  50 

O'Driscoll's  Treatment  of  Gold  Ores 8vo,  2  00 

*  Kerl's  Metallurgy— Copper  and  Iron 8vo,  15  00 

*  •'           "               Steel,  Fuel,  etc 8vo,  1500 

12 


Thurston's  Iron  and  Steel 8vo,  $3  50 

Alloys 8vo,  2  50 

Troilius's  Chemistry  of  Iron Svo,  2  00 

Kunbardt's  Ore  Dressing  in  Europe Svo,  1  50 

Weyrauch's  Strength  of  Iron  and  Steel.     (Du  Bois.) Svo,  1  50 

Beardslee  and  Kent's  Strength  of  Wrought  Iron Svo,  1  50 

Compton's  First  Lessons  in  Metal  Working 12mo,  1  50 

West's  American  Foundry  Practice 12mo,  2  50 

"      Moulder's  Text-book . .                                      12mo,  2  50 


MINERALOGY   AND  MINING. 

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Dana's  Descriptive  Mineralogy.     (E.  S.) Svo,  half  morocco,  12  50 

"      Mineralogy  and  Petrography.     (J.  D.) 12mo,  2  00 

"      Text-book  of  Mineralogy.     (E.  S.) Svo,  350 

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"      American  Localities  of  Minerals Svo,  1  00 

Brush  and  Dana's  Determinative  Mineralogy Svo,  3  50 

Rosenbusch's    Microscopical    Physiography   of    Minerals    and 

Rocks.     (Iddings.) Svo,  500 

Hussak's  Rock-forming  Minerals.     (Smith.) Svo,  2  00 

Willianis's  Lithology Svo,  3  00 

Chester's  Catalogue  of  Minerals Svo,  1  25 

"        Dictionary  of  the  Names  of  Minerals.. Svo,  3  00 

Egleston's  Catalogue  of  Minerals  and  Synonyms Svo,  2  50 

Goodyear's  Coal  Mines  of  the  Western  Coast 12mo,  2  50 

Kunhardt's  Ore  Dressing  in  Europe Svo,  1  50 

Sawyer's  Accidents  in  Mines Svo,  7  00 

Wilson's  Mine  Ventilation 16mo,  1  25 

Boyd's  Resources  of  South  Western  Virginia Svo,  3  00 

"      Map  of  South  Western  Virginia Pocket-book  form,  2  00 

Stockbridge's  Rocks  and  Soils Svo,  2  50 

^lissler's  Explosives — Nitroglycerine  and  Dynamite §vp,  4  00 

13 


*Drinker's  Tunnelling,  Explosives,  Compounds,  and  Rock  Drills. 

[4to,  half  morocco,  $25  00 

Beard's  Ventilation  of  Mines 12mo,  2  50 

Ihlseng's  Manual  of  Mining 8vo,  400 

STEAM  AND  ELECTRICAL  ENGINES,  BOILERS,  Etc. 

STATIONARY — MARINE — LOCOMOTIVE — GAS  ENGINES,  ETC. 

Weisbach's  Steam  Engine.     (Du  Bois.) 8vo,  500 

Thurston's  Engine  and  Boiler  Trials 8vo,  5  00 

"           Philosophy  of  the  Steam  Engine 12mo,  75 

Stationary  Steam  Engines 12mo,  1  50 

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"  Steam-boiler  Construction  and  Operation 8vo, 

"  Reflection  on  the  Motive  Power  of  Heat.    (Carnot.) 

12mo,  2  00 
Thurston's  Manual  of  the  Steam  Engine.     Part  I.,  Structure 

and  Theory 8vo,  7  50 

Thurston's  Manual  of  the   Steam  Engine.     Part  II.,    Design, 

Construction,  and  Operation 8vo,  7  50 

2  parts,  12  00 

Rontgen's  Thermodynamics.     (Du  Bois. ) 8vo,  5  00 

Peabody's  Thermodynamics  of  the  Steam  Engine 8vo,  5  00 

Valve  Gears  for  the  Steam-Engine 8vo,  2  50 

Tables  of  Saturated  Steam 8vo,  1  00 

Wood's  Thermodynamics,  Heat  Motors,  etc 8vo,  4  00 

Ptipin  and  Osterberg's  Thermodynamics 12mo,  1  25 

Kneass's  Practice  and  Theory  of  the  Injector 8vo,  1  50 

Reagan's  Steam  and  Electrical  Locomotives 12mo,  2  00 

Meyer's  Modern  Locomotive  Construction 4to,  10  00 

Whitham's  Steam-engine  Design 8vo,  6  00 

"          Constructive  Steam  Engineering 8vo,  10  00 

Hemenway's  Indicator  Practice 12mo,  2  00 

Fray's  Twenty  Years  with  the  Indicator Royal  8vo,  2  50 

Spangler's  Valve  Gears 8vo,  2  50 

*  Maw's  Marine  Engines Folio,  half  morocco,  18  00 

Trow  bridge's  Stationary  Steam  Engines ,.,.,.  .4to,  boards,  2.  50 

14 


Ford's  Boiler  Making  for  Boiler  Makers 18mo,  $1  00 

Wilson's  Steam  Boilers.     (Plainer.) 12mo,  2  50 

Baldwin's  Steani  Heating  for  Buildings 12mo,  2  50 

Hoadley's  Warm-blast  Furnace 8vo,  1  50 

Sinclair's  Locomotive  Running 12mo,  2  00 

Clerk's  Gas  Engine , 12mo,  4  00 

TABLES,  WEIGHTS,  AND  MEASURES. 

FOR  ENGINEERS,  MECHANICS,  ACTUARIES— METRIC  TABLES,  ETC.. 

Crandall's  Railway  and  Earthwork  Tables 8vo,  1  50 

Johnson's  Stadia  and  Earthwork  Tables 8vo,  1  25 

Bixby's  Graphical  Computing  Tables Sheet,  25 

Compton's  Logarithms 12mo,  1  50 

Ludlow's  Logarithmic  and  Other  Tables.     (Bass.) 12mo,  2  00 

Tlmrston's  Conversion  Tables 8vo,  1  00 

Egleston's  Weights  and  Measures 18mo,  75 

Totten's  Metr6logy 8vo,  2  50 

Fisher's  Table  of  Cubic  Yards Cardboard,  25 

Hudson's  Excavation  Tables.     Vol.  II 8vo,  1  00 

VENTILATION. 

STEAM  HEATING — HOUSE  INSPECTION — MINE  VENTILATION. 

Beard's  Ventilation  of  Mines 12mo,  2  50 

Baldwin's  Steam  Heating 12rno,  2  50 

Reid's  Ventilation  of  American  Dwellings 12mo,  1  50 

Mott's  The  Air  We  Breathe,  and  Ventilation 16nio,  1  00 

Gerhard's  Sanitary  House  Inspection Square  16ino,  1  00 

Wilson's  Mine  Ventilation 16mo,  1  25 

Carpenter's  Heating  and  Ventilating  of  Buildings 8vo,  3  00 

niSCELLANEOUS  PUBLICATIONS, 

Alcott's  Gems,  Sentiment,  Language Gilt  edges,  5  00 

Bailey's  The  New  Tale  of  a  Tub 8vo,  75 

Ballard's  Solution  of  the  Pyramid  Problem 8vo,  1  50 

Barnard's  The  Metrological  System  of  the  Great  Pyramid.  ,8.vp,  1  5.Q 

15 


*  Wiley's  Yosemite,  Alaska,  and  Yellowstone 4to, 

Emmon's  Geological  Guide-book  of  the  Rocky  Mountains.  .8vo, 

Fen-el's  Treatise  on  the  Winds Svo, 

Perkins's  Cornell  University Oblong  4to, 

Ricketts's  History  of  Rensselaer  Polytechnic  Institute 8vo, 

Mott's  The  Fallacy  of  the  Present  Theory  of  Sound.  .Sq.  16mo, 
Rotherham's    The    New    Testament    Critically  Emphathized. 

12nio, 

Totteu's  An  Important  Question  in  Metrology Svo, 

Whitehouse's  Lake  Mceris Paper, 

HEBREW  AND  CHALDEE  TEXT=BOOKS. 

FOR  SCHOOLS  AND  THEOLOGICAL  SEMINARIES. 

Gesenius's  Hebrew  and   Chaldee  Lexicon  to  Old   Testament. 

(Tregelles.) Small  4to,  half  morocco, 

Green's  Grammar  of  the  Hebrew  Language  (New  Edition). Svo, 

"       Elementary  Hebrew  Grammar 12mo, 

"       Hebrew  Chrestomathy Svo, 

Letteris's    Hebrew  Bible   (Massoretic  Notes  in  English). 

Svo,  arabesque, 

Luzzato's  Grammar  of  the  Biblical  Chaldaic  Language  and  the 
Talmud  Babli  Idioms 12mo, 

MEDICAL. 

Bull's  Maternal  Management  in  Health  and  Disease 12mo, 

Mott's  Composition,  Digestibility,  and  Nutritive  Value  of  Food. 

Large  mounted  chart, 

Steel's  Treatise  on  the  Diseases  of  the  Ox Svo, 

"      Treatise  on  the  Diseases  of  the  Dog Svo, 

Worcester's  Small  Hospitals — Establishment  and  Maintenance, 
including  Atkinson's  Suggestions  for  Hospital  Archi- 
tecture   12mo, 

Physiological  Chemistry.   (Handel.). Svo, 


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11 


1940 


SEP  19    1943 


LD  21-95m-7,'37 


YB  53822 


i : 


